1, 2-dihydro-1-hydroxy-1, 3, 5-triazines



causs methylallyl, Z-ethylallyl, I-methyl-Z-butenyl, 2-methyl-2-3,270,015 butneyl, 3-methyl-2-butenyl, 3-pentenyl, 2,3-dimethyl-2-1,2-DIHYDRO-1-HYDROXY-1,3,5-TRIAZINES Joseph J. Ursprung, Portage,Mich., assignor to The Upjohn Company, Kalamazoo, Mich., a corporationof Delaware No Drawing. Filed July 1, 1965, Ser. No. 468,945 29 Claims.(Cl. 260-2475) This application is a continuation-in-part of copendingapplication Serial No. 274,315, filed April 19, 1963, and now abandoned.

This invention relates to novel dihydrotriazines and to processes fortheir preparation, and is more particularly concerned with novel1,Z-dihydro-1-hydroxy-1,3,5-triabutenyl, 1,1,2-trilmethylallyl,1,3-dimethyl-2-butenyl, lethyl 2 'butenyl, 4 methyl 2 pentenyl, 2 ethyl-2 pentenyl, 4,4 dimethyl 2 pentenyl, 2 heptenyl, 2 octenyl, 5 octenyl,1,4 dimethyl 4 hexenyl, and the like. Examples of lower alkoxylalkyl are2- methoxyethyl, 2 ethoxyethyl, 2 butoxyethyl, 2-hexyloxyethyl, 2octyloxyethyl, 2 methoxypropyl, 3- methoxypropyl, 3 propoxypropyl, 2methoxy butyl, 3 ethoxybutyl, 4 butoxybutyl, 2 ethoxyhexyl, 3- mehoxy 3methylpentyl 4 methoxyoctyl, and the like. Examples of lower 'cycloalkylare cyclopropyl, 2- methylcyclopropyl, 2,2 dimethylcyclopropyl, 2,3dizines which can be represented by the formula: ethylcyclopropyl, 2butylcyclopropyl, cyclobutyl, 2- OH methylcyclobutyl, 3propylcyclobutyl, 2,3,4 triethylcyclobutyl, cyclopentyl, 2, 2dimethylcyclopentyl, 3-

R1 pentylcyclopentyl, 3 tert butylcyclopentyl, cyclohexyl, 4 tertbutylcyclohexyl, 3 isopropylcyclohexyl,

N543N 2,2 dimethylcyclohexyl, cycloheptyl, cyclooctyl, and

the like. Examples of lower aryl are phenyl, l-naphthyl,

I and Z-naphthyl. Examples of lower alkaryl are o-tolyl,

wherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, andlower haloaralkyl; wherein R is selected from the group consisting ofdi-lower-alkylamino, di-lower-alkenylamino, N-loweralkyllower-alkenylamino, and the heterocyclic moieties, aziridinyl,azetidinyl, pyrrolidinyl, piperidino, hexahydroazepinyl,heptamethylenimino, octamethylenimino, and morpholino, each of saidheterocyclic moities having attached as substituents on carbon atomsthereof zero to 3 lower alkyls, inclusive, the nitrogen atom of R beingthe point of attachment of R to the ring in said formula; and wherein Ris selected from the group consisting of hydrogen, lower alkyl, loweralkenyl, lower cycloalkyl, lower aryl, and lower aralkyl. R and R can bethe same or difierent. When R is di-lower-alkylamino ordi-loweralkenylalmino, the alkyls or the alkenyls therein can be thesame or different. When R is a heterocyclic moiety, the alkyls which canbe attached thereto can all be dilferent or any two or all of them canbe alike. When R and/or R are alkyl, they can be the same as ordifferent than any of the alkyls associated with R 7 The novel1,2-dihydro-l-hydroxy-1,3,5-triazines of the invention can berepresented by formulas other than Formula I.- Among these is:

m-tolyl, p-tolyl, m-ethylphenyl, p-tert-butylphenyl, the isomeric formsof xylyl, the isomeric forms of tri-methylphenyl, 4 methyl 1 naphthyl, 6propyl 2 naphthyl, 2,4,5,7-tetramethyl-l-naphthyl, and the like.Examples of lower aralkyl are benzyl, phenethyl, l-phenylethyl, hexyl, 5phenyl 2 methylpentyl, 1 naphthylmethyl, 2 (1 naphthyl)ethyl, 2 (2naphthylethyl), and the like. Examples of lower alkaralkyl areo-tolylmethyl, m tolylmethyl, p tolylmethyl, 4 tert butylphenylmethyl, 2(p tolyl)ethyl, l (m tolyl)ethyl, 3-(0- ethylphenyl)propyl, 4 methyl 1naphthylmethyl, 6 tert butyl 2 naphthylmethyl, and the like. Ex amplesof lower alkoxy aralkyl are 0 methoxybenzyl, m methoxybenzyl, pmethoxybenzyl, 2 (m methoxyphenyl)ethyl, 3 (p ethoxyphenyl)propyl,4-(ptert butoxyphenyl)butyl, 4 methoxy 1 naphthylmethyl, and the like.Examples of lower haloaralkyl are 0 chlorobenzyl, m fluorobenzyl, pbromolbenzyl, 2 (m iodophenyl)ethyl, 2,4 =dichlorobenzyl, 6- bromo 1naphthylmethyl, 4 (p chlorophenyl)butyl, and the like. Examples ofheterocyclic moieties within the scope of R in addition to those alreadymentioned above, are 2 methylaziridinyl, 2 ethylaziridinyl, 2-butylaziridinyl, 2,3 dimethylaziridinyl, 2,2 dimethylaziridinyl, 2methylazetidinyl, 3 methylazetidinyl, 2 octylazetidinyl, 2,2dimethylazetidinyl, 3,3 diethylazetidinyl, 2,4,4 trimethylazetidinyl,2,3,4 trilmethylazetidinyl, 2 methylpyrrolidinyl, 3 butylpyr- T,rolidinyl, 2 isohexylpyrrolidinyl, 2,3 dimethylpyrl-f l rolidinyl, 2,2dimethylpyrrolidinyl, 2,5 diethylpyr- N L, H rolidinyl, 3 tertbutylpyrrolidinyl, 2,3,5 trimethylpyrrolidinyl, 3,4 dioctylpyrrolidinyl,2 methylpiperi- IA dino, 3 methylpiperidino, 4 methylpiperidino, 3 iso-Formula IA is tautomeric with Formula I. For convenience, reference willbe made hereinafter only to Formula I. It is to be understood, however,that the novel compounds of this invention are likely to be mixtures oftautomeric forms, the compositions of which are dependent on suchfactors as the nature of R R and R and the environment. In someinstances, one form or another may predominate.

Examples of lower alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl octyl, and isomeric forms thereof. Examples of lower alkenyl arevinyl, allyl, propenyl, 2- butenyl, 3-methyl-2-butenyl, 3-pentenyl,-2,3-dimethyl-2 methylpropenyl, l-methylallyl, Z-methylallyl(methallyl), 2-butenyl (crotyl), 3-butenyl, 1, 2-dimethylallyl,1,1-dipropylpiperidino, 4 tert butylpiperidino, 2 methyl- 5ethylpiperidino, 3,5 dipentylpiperidino, 2,4,6 trimethylpiperidino, 2,6dimethyl 4 octylpiperidino, 2,3,5 triethylpiperidino, 2ethylhexahydroazepinyl, 4 tert butylhexahydroazepinyl, 3heptylhexahydroazepinyl, 2, 4 dimethylhexahydroazepinyl, 3,3dimethylhexahydroazepinyl, 2,4,6 tripropylhexahydroazepinyl, 2methylheptamethylenimino, 5 butylheptamethylenirnino, 2,4diisopropylheytamethylenimino, 3,3 diethylheptamethylenimino, 2,5,8trimethylheptamethylenimino, 3 methyloctamethylenimino, 2,9diethyloctamethylenin'lino, 4 isooctyloctamethylenimino, 2ethylmorpholino, 2 methyl 5 ethylmorpholino, 3,3 dimethylmorpholino, 2,6di tert butylmorpholino, and the like. In each of the above examples ofhet- [Ce Patented August 30, 1966 2 phenylpropyl, 4 phenylbutyl, 6phenylerocyclic moieties, the free valence, and hence the point ofattachment to a carbon atom of the triazine ring, is at the heterocyclicnitrogen atom.

The novel 1,2-dihydro-l-hydroxy-l,3,5-triazines of Formula I are aminesand exist either in the nonprotonated (free base) form or the protonated(acid addition salt) form depending upon the pH of the environment. Theyform stable protonates (monoor diacid addition salts) on neutralizationwith suitable acids, for example, hydrochloric, hydrobromic, sulfuric,phosphoric, nitric, acetric, benzoic, salicyclic, glycolic, succinic,nicotinic, tartaric, maleic, malic, pamoic, methanesulfonic,cyclohexanesulfamic, and lactic acids, and like pharmacologicallyacceptable acids.

The compounds of Formula I are orally and parenterally active in birdsand mammals, including man, an antihypertensive agents havingvasodilatory activity, and are useful for lowering blood pressure andfor the treatment of shock. They are also useful as antisecretory agentsand central nervous system depressants. For these purposes, they can beused in the nonprotonated (free base) form or in the protonated (acidaddition salt) form in association with a pharmaceutical carrier insolid or liquid dosage forms, such as tablets, capsules, powders, pills,granules, syrups, elixirs, suppositories, sterile aqueous or vegetableoil dispersions for parenteral use, and the like, alone or incombination with other drugs.

The novel 1,2-dihydro-1-hydroxy-1,3,5-triazines also form salts withthiocyanic acid which, when condensed with formaldehyde, form resinousmaterials useful as pickling inhibitors according to U.S. Patents2,425,320 and 2,606,155. They also form salts with fluosilicic acidwhich are useful as mothproofing agents according to US. Patents1,915,334 and 2,075,359. They can also be used for making aminoplastresins by condensation with formaldehyde. The acid addition salts arealso useful for upgrading the free bases.

The novel Formula I dihydrotriazines are prepared by oxidizing atriazine of the formula:

carboxylic acid. Particularly preferred for this purpose are theperbenzoic acids of the formula:

XII

III

wherein X is selected from the group consisting of halogen, lower alkyl,lower alkoxy, and nitro, and wherein n is from zero to 5, inclusive.However, other percarboxylic acids can be used for this oxidation.Examples of other suitable percarboxylic acids are performic acid,peracetic acid, perpropionic acid, perbutyric acid, perphthalic acid,percamphoric acid, and the like.

Triazines (guanamines) of Formula II are known in the art or can beprepared by methods known in the art [Smolin et al., s-Triazines andDerivatives, Interscience Publishers, Inc., New York, N.Y., pp. 222-33(1959)]. For example, they can be prepared by reacting a biguanide ofthe formula:

NH NH H mil-Nai- R: IV

wherein R and R are as given above, with a carboxylic acid ester, acarboxylic acid halide, a carboxylic acid anhydride, or a nitrile [e.g.,Shapiro et al., J. Am. Chem.

4 Soc. 79, 5064-71 (1957); Shapiro et al., I. Am. Chem. Soc. 81,3996-4000 (1959); Overberger et al., J. Am. Chem. Soc. 76, 1061-5(1954); Shapiro et al., J. Org. Chem. 26, 68-74, 3331-4 (1961);Cockburn, Can. J. Chem. 35, 1285-92 (1957); Bamberger et al., Ber. Deut.Chem. 25, 525-33 (1892); Thurston, US. Patent 2,427,- 314; Schaefer, US.Patent 2,777,848]. Illustratively, 2-anilino-4-dimethylamino-6-methyl-1,3,5-tiiazine is prepared by reacting1,1-dimethyl-5-phenylbi guanide (Formula IV; R =dimethylamino; R=phenyl) with acetyl chloride in the presence of sodium hydroxide [e.g.,Shapiro et al., J. Org. Chem. 26, 68-74 (1961)]. Further, 2-amino-4-methyl-6-piperidino-1,3,5-triazine is prepared by reacting1,1-pentamethylenebiguanide (Formula IV; R piperidino; R =hydrogen)first with acetic anhydride and then with sodium hydroxide [e.g.,Cockburn et al., Can. J. Chem. 35, 1285-92 (1957)].

Other examples of Formula IV biguanides suitable for preparing triazineswithin the scope of Formula II are 1,1- dimethylbiguanide,1,1-dicthylbiguanide, 1,1-dipropylbiguanide, 1,1-dibutylbiguanide, 1 1-di-tert-butylbi guanide, 1,1-diallylbiguanide,l-allyl-l-methylbiguanide, 1-ethyl1- (Z-methylallyl)-biguanide,1,1-di-4-hexenylbiguanide, 1,1- ethylenebiguanide,l,1-trimethylenebiguanide, 1,1-tetra- 'methylenebiguanide,1,1-(1,1-dimethyltetramethylene)biguanide,l,1-(2,3-dioctyltetramethylene)biguanide, 1,1-(4-ethyll-methylpentamethylene -biguanide, 1,1-( 1,3 ,5-trimethylphentamethylene biguanide, 1,1-hexamethylenebiguanide,1,1-octamethylenebiguanide, 1,1-(3-oxapentamethylene)biguanide,1,1,S-trimethylbiguanide, S-butyl-l, l-diethylbiguanide,1,1,5-trially1biguanide, l-allyl-S-cyclobutyl-l-ethylbiguanide,S-cyclohexyl-l,l-pentamethylenebiguanide,5-(2,6-dimethylphenyl)-l,l-(3-oxapentamethylene)-biguanide,1,1-diallyl-5-phenethylbiguanide, and the like. Other examples of acidhalides and anhydrides, and examples of esters and nitriles, which canbe reacted with biguanides within the scope of Formula IV to preparetriazines within the scope of Formula II are ethyl form-ate, ethylacetate, ethyl propionate butyryl chloride, methyl octanoate, ethylacrylate, acryloyl chloride, 4- hexenoyl chloride, methyl4-methyl-2-octenoate, ethyl 3- ethoxypropionate, isopropoxyacetonitrile,2-propoxypropionitrile, 3-methoxypropionyl chloride, methylcyclopropanecarboxylate, cyclohexanecarbonyl chloride, ethyl 4-tert-butylcyclohexanecarboxylate, methyl benzoate, p-toluoyl chloride,ethyl 2,6-dimethylbenzoate, ethyl l-naphthoate, ethyl phenyl-acetate,p-chlorobenzoyl chloride, methyl p-bromobenzoate, methylp-methoxyphenylacetate, ethyl o-ethylphenylacetate, propionic anhydride,butyric anhydride, and the like.

Biguanides of Formula IV suitable for preparing Formula II triazines,for example, each of the specific biguanides mentioned above, are eitherknown in the art or can be prepared by methods known in the art [e.g.,Shapiro et al., J. Am. Chem. Soc. 81, 372536, 3996-4000, 4635-9 (1959);Shapiro et al., J. Org. Chem. 26, 68-74 (1961); Detweiler et al., J. Am.Chem. Soc. 74, 1483-5 (1952); Oxley et al., J. Chem. Soc. 1252-6 (1951);Cockburn et al., Can. J. Chem. 35, 1285-92 (1957)]. For example,biguanides of Formula IV wherein R is hydrogen can be prepared byreacting cyanoguanidine (dicyandiamide) with a secondary amine salt, forexample, the hydrochloride, according to the equation:

wherein R is a given above. Illustratively, 1,1-pentamethylenebiguanidehydrochloride is prepared by heating a mixture of piperidinehydrochloride and cyanoguanidine [e.g., Shapiro et al., J. Am. Chem.Soc. 81, 3725-36 (1959)]. Big'uan-ides of Formula IV wherein R is givenabove and not hydrogen can be prepared by reacting a secondary aminesalt, e.g., the hydrochloride, with a 3-monosubstitutedl-cyanoguanidine, or by reacting a primary amine salt, e.g., thehydrochloride, with a 3,3-disubstituted l-cyanoguanidine, according tothe equations:

Illustratively, 1,1-dimethyl-5-propylbiguanide hydrochloride (FormulaIV; R =dimethylamino; R =propyl) is prepared either by heating a mixtureof dimethylamine hydrochloride and 1-cyano-3-propylguanidine or byheating a mixture of propylamine hydrochloride and l-cyano-3,3-dimethylguanicline [e.g., Shapiro et al., J. Am. Chem. Soc. 81,4635-9 (1959)]. 3-monosubstituted l-cyanoguanidines and3,3-disubstituted l-cyanoguanidines suitable for preparing Formula IVbiguanides as above described are known in the art or can be prepared bymethods known in the art, for example, by reacting a primary or asecondary amine with an alkali metal salt of dicyanimide [e.g., Shapiroet al., J. Am. Chem. Soc., 81, 4635-9 (1959); Redmon et al., US. Patent2,455,807].

Another method for preparing triazines within the scope of Formula IIstarts with the reaction of cyanuric chloride with one molecularequivalent of a Grignard reagent of the Formula R MgX, wherein R is agiven above (except hydrogen), thereby producing a triazine of theformula:

fiw R; C I, N

[Hirt et al., Helv. Chim. Acta 33, 1365-9 (1950); Overberger et al., I.Am. Chem. Soc., 79, 941-8 (1957)]. Then, one of the chlorines in theFormula V triazine is replaced with a primary amino group, i.e., NH or asecondary amino group, i.e., NHR and the other chlorine is replaced witha tertiary amino group, i.e., R wherein R and R are as defined above.These two replacements are accomplished by successive separate reactionsof the Formula V triazine with one molecular equivalent of ammonia or aprimary amine and with one molecular equivalent of a secondary amine, ineither order. These reactions are carried out by procedures known in theart to be useful for replacing the chlorines of ch1oro triazines withprimary, secondary, or tertiary amino groups [e.g., Hirt et al., Helv.Chim. Acta 33, 1365-9 (1950); Overberger et al., I. Am. Chem. Soc. 79,941-8 (1957); Thurston et al., J. Am. Chem. Soc., 73, 2981-3 (1951);Kaiser et al., J. Am. Chem. Soc., 73, 2984-6 (1951); Schaefer et al., J.Am. Soc., 77, 5918-2 (1955); Campbell et al., J. Org. Chem., 26, 2786-9(1961); Kaiser et al., US. Patent 2,653,934]. Illustratively, 2,4-dichloro-6-methyl-1,3,5-triazine is prepared by reacting cyanuricchloride with methylmagnesium bromide, and is transformed first to 2benzylamino-4-chloro-6-methyl- 1,3,5-triazine by reaction withbenzylamine, and then to 2benzylamino-4-diallylamino-6-methyl-1,3,5-triazine by reaction withdiallylamine. Alternatively, the 2,4-di- 6ch1oro-6-methyl-1,3,5-triazine is reacted first with diallylamine toproduce 2-chloro-4-diallylamino-6-methyl-1,3,5- triazine and then withbenzylamine to produce the same 2-benzylamino-4-diallyl-amino-6-methyl1,3,5 triazine (Formula II; R =methy1; R =diallylamino; R ==benzyl).Examples of suitable primary amines for this purpose are methylamine,ethylamine, propylamine, isopropylamine, .butylamine, secbutylamine,pentylamine, isopentylamine, hexylamine, heptylamine, octylamine,allylamine, 2-methylallylamine, Z-butenylamine, 3-butenylamine,3-pentenylamine, 4-hexenylamine, 4,4-dimethyl-2- pentenylamine,cyclobutylamine, cyclohexylamine, 4-tertbutylcyclohexylamine, aniline,l-naphthylamine, 2- naphthylamine, benzylamine, phenethylamine, and thelike. Examples of suitable secondary amines for this purpose aredimethylamine, diethylamine, N-methylethylamine, dipropylamine, Nethylisopropylamine, di secbutylamine, N-methylbutylamine,dipentylamine, N-ethyl- 2,4-dimethylpentylamine, N-methyloctylamine,diheptylamine, diallylamine, N-methylallylamine, di-1-methylallylamine,di-Z-methylallylamine, N-ethyl-l-methylallylamine,N-propyl-2-ethylallylamine, di-2-pentenylamine, di-3-butenylamine,di-4-hexenylamine, N-buty1-2-butenylamine, di(4-methyl-3-hexenyl)amine,aziridine, Z-methylaziridine, 2,2-dimethylaziridine, azetidine,2-ethylazetidine, 3-octylazetidine, 3,3-dimethylazetidine,2,2,4-trimethylazetidine, pyrrolidine, 2-propylpyrrolidine,3-butylpyrrolidine, 2 isohexylpyrrolidine, 2,3 dimethylpyrrolidine,2,2,4 trimethylpyrrolidine, 2,5 diethylpyrrolidine,3,4-dioctylpyrrolidine, piperidine, Z-methylpiperidine, 3-ethylpiperidine, 4-butylpiperidine, 2,4,6-trimethylpiperidine,2-methyl-S-ethylpiperidine, 3,5-dipentylpiperidine, hexahydroazepine,2-ethylhexahydroazepine, 4-tertbutylhexahydroazepine,3,3-dirnethylhexahydroazepine, 2,4,6- tripropylhexahydroazepine,heptamethylenimine, 2-methylheptamethylenimine, 2,4diisopropylheptamethylenimine, octamethylenimine,4-isooctyloctamethylenimine, morpholine, 2-ethylmorpholine,2-methyl-5-ethylmorpholine, 2,6-dimethylmorpholine, and the like.Examples of suitable Grignard reagents for this purpose aremethylmagnesium chloride, methylrnagnesium bromide, ethylmagnesiumchloride, propylmagnesium bromide, butylmagnesium chloride,isobutylmagnesium bromide, hexylmagnesium chloride, 3-pentenylm-agnesiumbromide, 4- hexenylmagnesium chloride, cyclopentylmagnesium bromide,cycloheylmagnesium chloride, 4-tertbutylcyclohexylmagnesium bromide,phenylmagnesium bromide, ptolylmagnesium iodide, benzylmagnesiumbromide, pethylbenzylmagnesium bromide, o methoxybenzylmagnesiumbromide, p-chlorobenzylmagnesium bromide, and the like.

Triazines within the scope of Formula II can also be prepared byreacting a triazine of the formula:

N RII 1-0 01;

(301: VI wherein R is as given above, first with ammonia or anappropriate primary amine, and then with an appropriate secondary amine[Kreutzberger, I. Am. Chem. Soc., 79, 2629-33 (1957); Shcroeder et al.,I. Am. Soc., 78, 2447-51 (1956)].- Lt desired, the replacement reactionscan be carried out first with the secondary amine, and then with ammoniaor the primary amine. Primary and secondary amines suitable for thispurpose are those listed above as being suitable for replacing thechlorines of dichlorotriazines (Formula V).

Percanboxylic acids suitable for the oxidation of Formula II tri-azinesto Forumla I l, 2-dihydro-1-hydroxy-1,3,5-triazines are known in the artor can be prepared by methods known in the art. With regard to thepreferred Formula III perbenzoic acids, see especially Braun, OrganicSyntheses, Coll. vol. I, 2d ed., 431

(1941) and Silbert et al., J. Org. Chem. 27, 1336-42 (1962). In FormulaIII, when n is 2 or more, the Xs can be the same or different. Examplesof halogen are fluorine, chlorine, bromine, and iodine. Examples oflower alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, and isomeric forms thereof. Examples of lower alkoxy are methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, beptyloxy, octyloxy, andisomeric forms thereof. Illustrative oxidizing acids of Formula II-Iincl-ude perbenzoic acid, o-, m-, and p-chloroand bromoperbenzoic acids,3,5-dichloroperbenzoic acid, 2,3, 5,6-tetrachloroperbenzoic acid,4-methylperbenzoic acid, 3,4-dimethylpenbenzoic acid,.pentamethylper-benzoic acid, m-, and p-methoxyper-benzoic acids,3-nitroperbenzoic acid, 2,4-dinitropenbenzoic acid, 3-chloro-4-methoxyperbenzoic acid, 3-chloro-4-ni-troperbenzoic acid, and the like.

In carrying out the reaction between the Formula II triazine and theFormula III .penbenzoic acid, the two reactants are mixed advantageouslybelow about 50 C., preferably between about and +10 C., although higheror lower temperatures can be used. It is preferred to mix the reactantsin the presence of an inert solvent and to stir the mixture until thereaction is substantially complete. Suitable solvents includeN-loweralkylpyrrolidones, e.g., N-methylpyrrolidone; lower alkanols,e.g., methanol, ethanol, propanol, isopropyl alco- 1101, the butanolsand the pentanols; lower alkanol and :glycol esters of lower alkanoicacids, e.g., ethyl acetate, butyl acetate, pentyl acetate, ethyleneglycol monoacetate, diethylene glycol monoacetate; ethers, e.g., diethylether, diisopropyl ether, ethylene glycol monoethyl ether, d-iethyleneglycol monobutyl ether; and the like. The molecular ratio of Formula IItriazine and Formula III perbenzoic acid can be varied widely. Ratiosfrom about 1:1 to 1:5, preferably from about 1:1.5 to 1:25, arespitable.

Many Formula II triazines with carbon-carbon double bond unsaturation inany or all of R R and R, can be oxidized to corresponding Formula I1,2-dihydro-1- hydroxyl-l,3,5-triazines without double bond epoxidation,particularly when the double bonds are part of lower 2-alkenylgroupings. If the double bonds are not resistant to epoxidation, theycan be protected before and regenerated after the oxidation. Forexample, a double bond can be brominated, the compound oxidized, and thedouble bond regenerated by treatment with zinc metal in a solvent suchas ethanol. Alternatively, epoxidation can be allowed to occur and theepoxy group transformed back to a double bond. An example is theprooedure of Cornforth et al., J. Chem. Soc., 112-27 (1959), involvingtreatment of an epoxide with a mixture of sodium iodide, sodium acetate,zinc, and acetic acid. Other methods of producing Formula I compoundswith carbon-carbon double bonds in an R R or R grouping involve startingwith Formula II triazines, one R R or R carbon atom of which is attachedto a halogen, e. g., bromine or iodine, another carbon atom vicinal tothat carbon atom being attached to a lower alkoxy, e.g., methoxy, or toa carboxyl. After the oxidation, the halogen plus lower alkoxy areremoved by zinc treatment [Dykstra et al., J. Am. Chem. Soc. 52, 3396-3404 (1930)], or the halogen plus canboxyl are removed by sodiumcarbonate treatment [Young et al., I. Am. Chem. Soc. 51, 2528-34(1929)]. Other methods of protecting, regenerating, or introducingcarbon-carbon double bonds to produce desired unsaturated Formula I1,2-dihydro-l-hydroxy-l,3,5-triazines will be apparent to those skilledin the art.

The 1,Z-dihydro-l-hydroxy-l,3,5-triazine of Formula I can be isolatedfrom the oxidation reaction mixture by conventional techniques, forexample, by successive evaporation of the reaction solvent at reducedpressure, solution of thebasic Formula I product in aqueous acid, c.g.,hydrochloric acid, removal of undesired water-insoluble reactionproducts by filtration, neutralization of the acidic filtrate, andisolation of the Formula I product by filtration, extraction, orchromatography. The isolated material can be purified by conventionaltechniques, for example, by recrystallization from a suitable solvent orpair of solvents, or by preparation of an acid addition salt, e.g., thehydrochloride or acid phosphate, and recrystallization of the salt,followed, if desired, by reconversi-on of the salt to the free base inthe usual manner.

1,2-dihydro-l-hydroxy-l,3,5-triazines within the scope of Formula I andcontaining one or more lower alkenyls can be transformed byhydrogenation to other Formula I products containing lower alkyls inplace of the lower alkenyls. In this process, each lower alkenyl ishydrogenated to the corresponding lower alkyl. The Formula I reactant isnot otherwise altered by the hydrogenation. For example, a Formula Icompound wherein R is vinyl, or wherein R is diallylamino, or wherein Ris allyl is transformed to the corresponding formula I compound whereinR is ethyl, or wherein R is dipropylamino, or wherein R is propyl. Moreprecisely, a 1,2-dihydrol-hydroxy-l,3,5-triazine product of the formula:

(In-I Rs VI wherein R is selected from the group consisting of hydrogen,lower alkyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl, loweralkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, and lowerhaloaralkyl; wherein R is selected from the group consisting ofdi-lower-alkylamino and the heterocyclic moieties, aziridinyl,azetidinyl, pyrrolidinyl, piperidino, hexahydroazepinyl,heptamethylenimino, octamethylenimino, and morpholino, each of saidheterocyclic moieties having attached as substituents on carbon atomsthereof zero to 3 lower alkyls inclusive, the nitrogen atom of R beingthe point of attachment of R to the ring in said formula; and wherein Ris selected from the group consisting of hydrogen, lower alkyl, lowercycloalkyl, lower aryl, and lower aralkyl, with the proviso that atleast one lower alkyl be present in said1,2-dihydro-l-hydroxy-l,3,5-triazine product in addition to the loweralkyls which can be attached to a heterocyclic moiety, can be preparedby hydrogenating a Formula I, l,3-dihydro-l-hydroxy-1,3,5-triazinereactant, wherein R R and R are as defined above, with the proviso thatat least one lower alkenyl group be present in said reactant.

This hydrogenation is preferably carried out in the presence of ahydrogenation catalyst, for example, a noble metal, e.g., platinum,palladium, rhodium, or a base 'metal, e.g., Raney nickel, Raney cobalt,and in the presence of an inert solvent, for example, methanol, ethanol,dioxane, ethyl acetate, and the like. Hydrogenation pressures rangingfrom about atmospheric to about 50 p.s.i., and hydrogenationtemperatures ranging from about 10 to about C. are preferred. The 1,2-dihydro-l-hydroxy-l,3,5-triazine product can be isolated by conventionaltechniques, for example, by filtration of the catalyst and evaporationof the solvent, and can be purified as described above.

The 1,2-dihydro-l-hydroxy-l,3,5-triazines of Formula I are transformedto monoacid and diacid addition salts by neutralization with appropriateamounts of the corresponding inorganic or organic acid, examples ofwhich are \given above. These transformations can be carried out by avariety of procedures known to the art to be generally useful for thepreparation of amine acid addition salts. The choice of the mostsuitable procedure will depend on a variety of factors includingconvenience of operation, economic considerations, and particularly thesolubility characteristics of the Formula I amine, the

acid, and the acid addition salt. If the acid is soluble in water, thebasic compound of Formula I can be dissolved in water containing eitherone or two equivalent amounts of the acid, and thereafter, the water canbe removed by evaporation. If the acid is soluble in a relativelynon-polar solvent, for example, diethyl ether or diisopropyl ether,separate solutions of the acid and the basic Formula I compound in sucha solvent can be mixed in equivalent amounts, whereupon the acidaddition salt will usually precipitate because of its relatively lowsolubility in the non-polar solvent. Alternatively, the basic Formula Icompound can be mixed with the acid in the presence of a solvent ofmoderate polarity, for example, a lower alkanol, a lower alkanone, or alower alkyl ester of a lower alkanoic acid. Examples of these solventsare ethanol, acetone, and ethyl acetate, respectively. Subsequentadmixture of the resulting solution of acid addition salt with a solventof relatively low polarity, for example, diethyl ether or hexane, willusually cause precipitation of the acid addition salt.

The 1,Z-dihydro-l-hydroxy-Z-imino-1,3,5-triazines of Formula I, whereinR is hydrogen, also form carboxyacylates on treatment withcarboxyacylating agents, for example, carboxylic acid anhydrides andcarboxylic acid chlorides. These carboxyacylates are amines, and existin either the nonprotonated (free base) form or the protonated (acidaddition salt) form depending upon the pH of the environment. They formstable protonates on neutralization with suitable acids, for example,those listed above as suitable for the formation of acid addition saltsof the Formula I dihydrotriazines.

These carboxyacylates and their acid addition salts are active in birdsand mammals, including man, as antihypertensive agents havingvasodilating activity, and are useful for lowering blood pressure andfor the treatment of shock. The carboxyacylates can also be used forupgrading a Formula I dihydrotriazine free base by transformation of thelatter to a carboxyacylate, purification of the carboxyacylate, and thenremoval of the carboxyacyl moiety or moieties, advantageously byalcoholysis. The carboxyacylate acid addition salts can also be used forupgrading the carboxyacylate free bases.

Although substantially any carboxyacylating agent can be used to producethese carboxyacylates, especially suitable are the anhydrides, mixedanhydrides, and acid chlorides of alkanoic, cycloalkanoic, alkenoic,cycloalkenoic, aralkanoic, aromatic, and heterocyclic carboxylic acids.These anhydrides and acid chlorides can also be substituted with any ofa wide variety of atomic or molecular moieties unreactive with thedihydrotriazine reactants. Examples of such substituents are alkyl,e.g., methyl, butyl, decyl; alkoxy, e.g., methoxy, ethoxy, pentyloxy;alkylthio, e.g., methylthio, propylthio, heptylthio; dialkylamino, e.g.,dimethylamino, diethylamino, dihexylamino; alkoxycarbonyl, e.g.,methoxycarbonyl, propoxycarbonyl, nonoxycarbonyl; carboxyacyl, e.g.,acetyl, butyryl; carboxamido, e.g., benzamido, acetamido; nitro; fiuoro;cyano; and the like. Chlorine, bromine, and iodine can also besubstituents on aromatic portions of the carboxyacylating agents.

Examples of suitable anhydrides are acetic anhydride, propionicanhydride, butyric anhydride, isobutyric anhydride, acrylic anhydride,crotonic anhydride, cyclohexanecarboxylic anhydride, benzoic anhydride,naphthoic anhydride, furoic anhydride, and the like, as well as thecorresponding anhydrides substituted with one or more of theabove-mentioned substituents. Examples of suitable acid chlorides areacetyl chloride, propionyl chloride, butyryl chloride, isobutyrylchloride, decanoyl chloride, acryloyl chloride, crotonoyl chloride,cyclohexanecarbonyl chloride, 3-cyclohexenecarbonyl chloride,phenylacetyl chloride, succinyl chloride, benzoyl chloride, naphthoylchloride, furoyl chlonide, 3'pyridinecarbonyl chloride, phthaloylchloride, and the like, as well as the cor- 10 responding acid chloridessubstituted with one or more of the above-mentioned substituents.

The carboxyacylate is produced by mixing the 1,2-dihydro l-hydroxy2-imino 1,3,5-triazine (Formula I, R =H) with an appropriate amount ofthe anhydride or acid chloride, preferably in the presence of a diluent.The carboxyacylation usually takes place rapidly in the range about 20to about +50 C. Suitable diluents are ethers, e.g., diethyl ether andtetrahydrofuran; ketones,

e.g., acetone and methyl ethyl ketone; esters, e.g., methyl acetate andethyl acetate; acetonitrile, pyridine, and the like.

The carboxyacylate obtained depends on such factors as the nature of thedihydrotriazine reactant, the nature and amount of carboxyacylatingagent, the reaction time, and the reaction temperature. An N-monocylate,an O,N-d-iacylate, or a mixture of those is usually obtained. Relativelylow reaction temperatures, i.e., about -20 to about 20 C., andrelatively short reaction times, i.e., a few seconds to about 10minutes, usually favor production of the N-monoacylate. Highertemperatures, i.e., about 30 to about 50 C., and longer reaction times,i.e., about 30 minutes to several hours, usually favor production of theQ'N-di-acylate.

At least one molecular equivalent of carboxyacylating agent should beused for the introduction of each carboxyacyl moiety into a Formula 'Idihydrotriazine (R =H). A substantial excess of craboxyacylating agent,i.e., about 4 to about 25 molecular equivalents, should usually be usedfor production of an O,N-diacylate.

The desired carboxyacylate usually separates from the reaction mixturein crystalline form as an acid addition salt. The hydrochloric acidaddition salt is obtained when a carboxylic acid chloride is used as acarboxyacylating agent. When a carboxylic acid anhydride is used as acarboxyacylating agent, the corresponding organic carboxylic acidaddition salt is obtained. These salts can be separated from thereaction mixture in the usual manner, for example, 'by filtration orcentrifugation. Alternatively, the diluent can be evaporated, preferablyat reduced pressure. The resulting acid addition salt can then -bepurified if desired by conventional techniques, for example, byrecrystallization from a suitable solvent or mixture of solvents.

The free base form of the carboxyacylate can be obtained byneutralization of the acid addition salt by another base of similar orslightly greater strength, e.g., ammonia or an alkyl-, d-i-alkyl-, ortrialkylamine. Especially useful for that purpose is triethylamine.Advantageously, the acid addition salt is dissolved in a solvent ofmoderate polarity, e.g., ethanol, and sufiicient triethylamine is addedto neutralize the acid. Excess triethylamine should be avoided. Theresulting free base can be isolated and purified by conventionalmethods, for example, evaporation of the solvent and recrystallizationfrom a suitable solvent or mixture of solvents. The free base can then,if desired, be transformed to a ditferent acid addition salt byneutralization with an organic or inorganic acid.

carboxyacylates obtained from Formula -I dihydrotriazines can berepresented by the formula:

VIII

wherein R is selected from the group consisting of hydro gen, loweralkyl, lower alkenyl, lower alkoxy-alkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, andlower haloaralkyl; wherein R is selected from the group consisting ofdilower-alkylamiino, di-lower-alkenylamino,N-lower-alkyllower-alkenylamino, and the heterocyclic moieties,aziridinyl, 'azetidinyl, pyrrolidinyl, piperidino, hexahydroazepinyl,heptamethylenimino, octamethylenimino, and morpholino, each of saidheterocyclic moieties having attached as substituents on carbon atomsthereof zero to 3 lower alkyls, inclusive, the nitrogen atom of R beingthe point of attachment of R to the ring in said formula; wherein A iscar boxy acyl, and wherein A is selected from the group consisting ofhydrogen and carboxyacyl.

The dihydrotriazine carboxyacylates of Formula VIII can be representedby other formulas. For example, when A is hydrogen, the carboxyacylatescan be represented by Formula VIII A:

Compounds of Formula VIII A are tautome-ric with Formula VIII compoundswherein A is hydrogen. These carboxyacylates are likely to be mixturesof tautomeric forms, the compositions of which are dependent on suchfactors as the nature of the su-bstituents and the carboxyacyl moiety,and the environment. In some instances, one form or another maypredominate. Formula VIII is used for convenience, and the other formsare not excluded.

Di-hydrotriazine carboxyacylates prepared as described above are easilytransformed back to the Formula I dihydrotriazine, preferably by warmingwith a lower alkanol, e.g., methanol or ethanol. Simultaneous treatmentwith a base, for example, gaseous ammonia, usually acoelerates thealcoholysis.

The invention can be more fully understood by the following examples.

EXAMPLE 1 Part A.2-amin04-a'iallylamina-I,3,5-triazine Sodium metal (4.6g.; 0.20 gram atom) was reacted with 100 m1. of methanol, and themixture was added to a stirred solution of 1,1-diallylbiguanidehydrochloride (21.8 g.;.0.l mole) in 50 ml. of methanol at about 25 C.Ethyl formate (7.4 g.; 0.10 mole) was then added to the resultingstirred mixture during 5 minutes at 25 C. After stirring for anadditional 48 hours at 25 C., the solvent was removed under reducedpressure and about 50 ml. of water was added to the residue. Thecolorless needles which formed were filtered and recrystallized from amixture of ethanol and water to give 11.6 g. of2-amino-4-diallylamino-1,3,5-triazine; M.P. 113-116 C.

Analysis.Calcd. for C H N C, 56.52 H, 6.85; N, 36.63. Found: C, 56.69;H, 6.98; N, 37.16. I.R.- (Principal bands; mineral oil mull) 3380, 3330,3160, 1660, 1645, 1585, 1550, 1515, 1240, 1190, 815 cmr PartB.--1,2-dihydro-1 -hydroxy-4-dialIyIamin0-2-imino- 1,3,5-triazine Asolution of perbenzoic acid (6.9 g.; 0.05 mole) in 50 m1. of ethanol wasadded gradually during 20 minutes to a stirred suspension of2-amino-4-diallylamino-1,3,5- triazine (5.1 g.; 0.027 mole) in 150 ml.of ethanol at 5 C. The resulting mixture was stirred for 18 hours at 05C. Solvent was evaporated under reduced pressure, and a solution of ml.of concentrated hydrochloric acid in ml. of water was added to theresidue. The resulting suspension was filtered, the filter cake beingwashed twice with 50-ml. portions of water. The combined filtrate andwashings were adjust to pH 9 with aqueous 50% sodium hydroxide solution.The solid which separated was filtered and washed with 50 ml. of water.The filtrate and washings were combined and extracted with twelve250-ml. portions of chloroform. The chloroform extracts were combinedand dried with sodium sulfate. Evaporation of the chloroform gave asolid residue which was recrystallized from acetonitrile to give 2.3 g.of 1,2- dihydro 1 hydroxy 4 diallylamino 2 imino- 1,3,5-triazine; M.P.139-14l C.

Analysir.-Calcd. for C H N O: C, 52.16; H, 6.32. Found: C, 52,34; H,5.98 U.V.(H O) 255 m (e=15,850); 315 m (5:5,850). (0.01 N HCl) 229 mi(e=20,200); 245 m (sh) (e=14,450); 280 m (sh) (e=2,950). (0.01 N KOH)255 m (e=l5,250); 315 my (5:5,800). I.R.-(Principal bands; mineral oilmull) 3380, 1665, 1606, 1510, 1480, 1255, 1165, 1115, 1102 cmf Additionof absolute ethanol containing one equivalent of hydrogen chloride to anabsolute ethanol solution of 1,2 dihydro 1 hydroxy 4 diallylamino 2imino- 1,3,5-triazine followed by addition of about 4 volumes of diethylether gives the triazine monohydrochloride. Use of 2 equivalents ofhydrogen chloride in this procedure gives the dihydrochloride. Similaruse of one equivalent of benzoic acid gives the monobenzoic acidaddition salt.

EXAMPLE 2 Part A.2-amin0-4-diallylamin0-6-metl1yl-1,3,5-triazinc Sodiummetal (3.45 g.; 0.15 gram atom) was reacted with 50 ml. of methanol, andthe mixture was added to a stirred solution of 1,1-diallylbiguanidehydrochloride (16.6 g.; 0.076 mole) in ml. of methanol at about 25 C.Ethyl acetate (7.0 g.; 0.08 mole) was then added to the resultingstirred mixture. After stirring for an additional 40 hours at 25 C., 300ml. of water was added. The solid which precipitated on cooling wasfiltered and dried to give a solid (9.0 g.; M.P. 68-70 C.) which, onrecrystallization from a mixture of methanol and water, gave 8.5 g. of2-amino-4-diallylamino-6- methyl-1,3,5-triazine in the form of colorlessneedles; M.P. 81-82 C.

Analysis.-Calcd. for C H N C, 58.51; H, 7.37; N, 34.12. Found: C, 58.98;H, 7.24; N, 33.74 I.R.- (Principal bands; mineral oil mull) 3310, 3120,1530, 1240, 1040, 815 cmr Part B.-1,2-dihydro-1-lzydr0xy-4-diallyIamin0-2-imino- 6-met/zyl-1 ,3 ,5 -triazzne Followingthe procedure of Example 1, Part B, 2- amino 4 diallylamino 6 methyl1,3,5 triazine (5.1 g.; 0.025 mole) was oxidized with perbenzoic acid(6.9 g.; 0.05 mole) in 50 ml. of ethanol. Recrystallization of theproduct from acetonitrile gave 3.65 g. of 1,2-tridihydro 1 hydroxy 4diallylamino 2 imino 6- methyl-1,3,5-triazine; M.P. 132-134 C. Twoadditional recrystallizations from acetonitrile gave 3.0 g. of the sameproduct with the same melting point.

Analysis.-Calcd. for C H N O: C, 54.28; H, 6.83; N, 31.66. Found: C,54.12; H, 6.64; N, 31.05 U.V. (H 0) 255 m (e=l6,950); 305 m (e=5,900).(0.01 NHCl) 226 my. (=17,350); 239 m (e=16,950); 270 m (sh) (e=6,450).(0.01 N KOH) 255 my. (e=l7,200); 305 m (e=4,750). I.R.-(Principal bands;mineral oil mull) 3395, 1658, 1642, 1595, 1545, 1520, 1486, 1260, 1178,1140, 1070, 1005 cm.-

EXAMPLE 3 J ,Z-dz'h ydro-I -hydroxy-4 -di propy lam ino-Z-imin0-6-methyl-1,3,5-triazine A mixture of 1,2 dihydro 1 hydroxy 4diallylamino-2-imino-6-methyl-1,3,5-triazine (1.00 g.; 0.0045 mole), 25ml. of ethanol, and 10 mg. of platinum oxide was shaken with hydrogen at50 lbs. initial pressure for 10 minutes at 25 C. The decrease inhydrogen pressure indicated uptake of 0.009 mole of hydrogen. Afterremoval of catalyst by filtration, solvent was removed under reducedpressure and the residue was recrystallized twice from acetonitrile togive 0.65 g. of 1,2-dihydro-lhydroxy 4-dipropylamino 2 imino 6 methyl1,3,5- triazine; M.P. -147 C.

Analysis.Calcd. for C H N O: C, 53.31; H, 8.50. Found: C, 53.81; H,8.04. U.V.(H 211.5 m (e=20,800); 255 m (e=l6,650); 305 m (e=5,100).(0.01 N H 50 227 m (e=l6,850); 241 m (e=l5,600); 280 m (sh.) (e=4,350).(0.01 N KOH) 255 m (e=l6,550); 304 mp (e=5,100). I.R.(Principal band;mineral oil mull) 3300, 1690, 1660, 1590, 1525, 1175, 1105, 1080, 1035,1015, 775 cmr N.M.R.The nuclear magnetic resonance spectrum of thiscompound was observed in deuterochloroform on a Varian A-60spectrophotometer. The following absorption frequencies measured incycles per second were observed downfield from tetramethylsilane whichwas arbitrarily set at 0 c.p.s. Typical dipropylamine absorption wasfound at 53 c.p.s. (triplet, 6 protons), 95 c.p.s. (quintuplet, 4protons) and 207 c.p.s., triplet, 4 protons). A band at 154 c.p.s.(singlet, 3 protons) was found for the CH group on the triazine ring andabsorption at 460 c.p.s. (broad singlet, 2 protons) is due to the twohydrogens on nitrogen and oxygen.

EXAMPLE 4 Part A .--2-amin0-4-dially lam ino-6-ethyl-1 ,3,5-triazineSodium metal (18.4 g.; 0.80 gram atom) was reacted with 300 ml. ofmethanol, and the mixture was added to a stirred solution of1,1-diallylbiguanide hydrochloride (87.0 g.; 0.40 mole) in 300 m1. ofmethanol at about 25 C. Ethyl propionate (44.9 g.; 0.44 mole) was thenadded to the resulting stirred mixture at 25 C. After stirring for 71hours at 25 C., the reaction mixture was diluted with 2000 ml. of waterand cooled. The solid which precipitated was filtered and recrystallizedfrom a mixture of methanol and water to give 57.1 g. of2-amino-4-diallylamino-G-ethyl-1,3,5-triazine in the form of whitecrystals; M.P. 6566 C.

Analysis.-Calcd. for C H N C, 60.25; H, 7.81. Found: c, 60.40; H, 7.34.U.V.(C H =,OH) 213 mp (e=26,700); 262 m (e=4,950). I.R-(Principal bands;mineral oil mull) 3315, 3130, 1669, 1560, 1525, 1229, 1051 cm.-

Part B.1,2-dihydr0-1-hydroxy 4-diallylamin0-6-ethyl- 2 -imin0-I ,3,5-triazine Finely-divided m-chloroperbenzoic acid (95% pure; 9.0 g.; 0.05mole) was added gradually during 20 minutes to a stirred solution of2-amino-4-diallylamino-6-ethyl- 1,3,5-triazine (5.5 g.; 0.025 mole) in150 ml. of absolute ethanol at C. The resulting reaction mixture wasstirred 8 hours at 0-5 C. and hours while rising gradually to C. Solventwas removed at reduced pressure, and a solution of 5 ml. of concentratedhydrochloric acid in 200 ml. of water was added to the white solidresidue. This mixture was filtered. The filter cake was washed withwater, and the combined filtrate and washings were adjusted to pH 9 withaqueous sodium hydroxide solution. The yellow oil which formed wascollected and crystallized from a mixture of methanol and water to give1.0 g. of unreacted starting triazine; M.P. 63-66 C. The aqueousalkaline solution was extracted with ten 100-ml. portions of chloroform.These extracts were combined, dried, and evaporated to give a yellow oilwhich crystallized and was recrystallized twice from acetonitrile togive 2.0 g. of 1,2-dihydro-1-hydroxy-4-diallylamino-6-ethyl-2-imino-1,3,5-triazine in the form of light-yellow needles whichgave a dark brown ferric chloride test; M.P. 108.5-110" C.

Analysis.Calcd. for C H N O: C, 56.15; H, 7.28; N, 29.77; 0, 6.80.Found: C, 55.88; H, 7.39; N, 29.06; 0, 7.42. U.V.(H O) 255 m (e=l6,000);305 m (E=5,700). (0.01 N HCl)) 226 m e=l6,800); 241 m (e=l5,200); 260 mp(sh.) (e=7,700). (0.01 N KOH) 255 m (e=15,200); 305 m (5:5,450).I.R.-(Principal bands; mineral oil mull) 3280, 3070, 1689, 1657, 1584,1520, 1256, 1162 cmf Addition of absolute ethanol containing oneequivalent of hydrogen chloride to an absolute ethanol solution of 1,Z-dihydro-1-hydroxy-4-diallylamino-6-ethyl-2-imino-1,3, 5-triazinefollowed by addition of about 4 volumes of diethyl ether gives thetriazine monohydrochloride. Use of 2 equivalents of hydrogen chloride inthis procedure gives the dihydrochloride. Similar use of one equivalentof benzoic acid gives the monobenzoic acid addition salt.

EXAMPLE 5 Part A .2-amin0-4-methyl-6-m0rpoh0lino-1,3,.5-triazine Sodiummetal (9.7 g.; 0.42 gram atom) was reacted with 300 ml. of methanol, andthe mixture was added rapidly to a stirred solution of1,1-(3-oxapentamethylene) biguanide hydrochloride (43.5 g.; 0.21 mole)in ml. of methanol at 25 C. Ethyl acetate (21.1 g.; 0.24 mole) was thenadded to the resulting stirred mixture at 25 C. After stirring for 51hours at 25 C., the mixture was diluted with water to 2 liters and theresulting precipitate was filtered. Additional precipitate was obtainedby concentrating the filtrate first to about 1000 ml. and then to about100 ml., cooling and filtering after each concentration. The combinedprecipitates were recrystallized from water to yield 25.7 g. of white,solid 2-amino-4- methyl-6-morpholino-1,3,5-triazine; M.P. 184-185 C.(sublimes slowly).

Analysis.--Calcd. for C H N O: C, 49.22; H, 6.71. Found: C, 48.71; H,6.23. U.V.(H O) 214 mp (5:23.350 226 mp. (sh.) (e=2l,200); 261 mp.(s=4,650). I.R.--(Principal bands; mineral oil mull) 3385, 3140, 1656,1567, 1545, 1525, 1243, 1112, 1103, 1065 cm.-

Part B.-I,2-dihydr0-1-hya'roxy-2-imino-6-methyl-4-morpholin0-1,3,5-triazine Following the procedure of Example 4, Part B,2- amino-4-methyl-6-morpholino-1,3,5-triazine (4.9 g.; 0.025 mole) wasoxidized with m-chloroperbenzoic acid (95% pure; 9.0 g.; 0.05 mole) inml. of absolute ethanol. The residue obtained from the combinedchloroform extracts was recrystallized from acetonitrile to give 0.7 g.of 1,2-dihydrol -hydroxy-Z-imino-6-methyl-4-morpholino- 1,3,5-triazinein the form of a white solid; M.P. 254- 255 C.

Analysis.Calcd. for C H N O C, 45.49; H, 6.20. Found: C, 44.97; H, 5.73.U.V.-(H O) 256 m (s=l6,050); 305 m (e=5,500). (0.01 N HCl) 227 m(e=l6,650); 242 m (e=15,450). (0.01 N KOH) 256 m (e=l6,000); 305 m(e=5,500). l.R.-Principa1 bands; mineral oil mull) 3400, 1665, 1575,1525, 1480, 1260, 1173, 1115 cmr Addition of absolute ethanol containingone equivalent of hydrogen chloride to an absolute ethanol solution of1,2-dihydro l-hydroxy-Zdmino 6-methyl-4-morpholino- 1,3,5-triazinefollowed by addition of about 4 volumes of diethyl ether gives thetriazine monohydrochloride. Use of 2 equivalents of hydrogen chloride inthis procedure gives the dihydrochloride. Similar use of one molecularamount of phosphoric acid gives the monophosphoric acid addition salt.

EXAMPLE '6 chloride is fused with 3-cyclohexyl-l-cyanoguanidine to yieldS-cyclohexyl-1,1-ethy1enebiguanide hydrochloride.

Part B.2-(1-azz'ridinyl)-4-cycl0hexylamin0- 6-m ethyl-1 ,3 ,5 -triazineFollowing the procedure of Example 5, Part A, 5-cyclohexyl-l,l-ethylenebiguanide hydrochloride is reacted with ethylacetate in the presence of sodium methoxide and methanol to give2-(1-aziridnyl)-4-cyclohexylamino-ti-methyl-1,3,5-triazine.

Port C.1,2-dihydro-1-hydr0xy-4- I-aziridinyl) -2-cyclhexyIimino-6-methyl-I ,3,5-triazine Following the procedure ofExample 4, Part B, 2-(1- aziridinyl)-4-cyclohexylamino6-methyl-l,3,5-triazine is oxidized with m-chloroperbenzoic acid to give1,2-dihydro-l-hydroxy 4-(l-aziridinyl) 2-cyclohexylimino-6-methyl-1,3,5-triazine.

EXAMPLE 8 Part A.2-amino-4-benzyl-6-diallyIamin0-1,3,5-zriazine Sodiummetal (9.2 g.; 0.40 gram atom) was reacted with 300 ml. of ethanol, andthe mixture was added rapidly to a stirred solution of1,1-diallylbiguanide hydrochloride (43.5 g.; 0.20 mole) in 100 ml. ofethanol at about 25 C. Ethyl phenylacetate (36.1 g; 0.22 mole) was thenadded to the resulting stirred mixture at 25 C. After stirring for 54hours at 25 C., the reaction mixture was diluted to 2000 ml. with waterand cooled. The solid which precipitated was filtered and recrystallizedfrom a mixture of methanol and water to give 28.7 g. of 2-amino-4-benzyl-6-diallylamino-1,3,5-triazine, M.P. 58-60 C.

AnaIysis.-Calcd. for C I-I N C, 68.30; H, 6.81; N, 24.89. Found: C,68.26; H, 6.99; N, 24.18. U.V.- (C H OH) 211 m (E=33,600); 265 m (64,900). l.R.-(Principa1 bands; mineral oil mull) 3365, 3310, 3205, 3155,3090, 3030, 1642, 1535, 1495, 1256, 1193, 1146, 760, 711, 686 cm.-

Part B.] ,2-dihydr0-I-hydroxy-6-benzyl-4-diaIlylamino-Z-imino-I,3,5-triazine Following the procedure of Example4, Part B, 2-ami- 'no-4-benzyl-6-dia1lylamino-1,3,5-t-riazine (7.0 g.;0.025

mole) was oxidized with m-chloroperbenzoic acid (95% pure; 9.0 g.; 0.05mole) in 150 ml. of absolute ethanol. There was obtained1,2-dihydro-1-hydroxy-6-benzyl-4- diallylamino-Z-imino-l,3,5-triazine inthe form of an oil which did not crystallize and which gave a positiveferric chloride test.

U.V.-(H O) 259 mu (e=11,650); 310 mu (e=3,250). (0.01 N HCl) 225 m(e=17,550); 242 mu s=14,400). (0.01 N KOH) 259 m (e=1l,650); 307 m(6=3,650).

EXAMPLE 9 Part A .2-aminc-4-butyl-6-diallylamino-1,3,5-triazineFollowing the procedure of Example 8, Part A, 1,1- diallylbiguanidehydrochloride (43.5 g.; 0.20 mole) was reacted with ethyl valerate (28.6g.; 0.22 mole) in the presence of sodium ethoxide and ethanol. A 48-hourreaction time was used. The oil which separated on dilution of thereaction mixture with water crystallized on cooling at about 5-10 C. for4 days. This material was recrystallized from a mixture of methanol andwater at 0 C. to give 35.8 g. of2-amino-4-butyl-6-diallylamino-1,3,5-triazine in the form of whitecrystals; M.P. 32-34 C.

AnalySiS.Ca1Cd. for C13H21N51 C, H, N, 28.32. Found: C, 63.36; H, 8.94;N, 27.95. U.V.- (C,H OH) 214 m (e=26,100); 231 mu (sh.) (e=22,800); 263m (e=5,400). I.R.(Principa1 bands; mineral oil mull) 3495, 3320, 3150,3090, 1645, 1560, 1535, 1305, 1246, 1196 cmr PartB.1,Z-dihydro-I-hydroxy-6-butyl-4- diallylwmino-2-imino-l,3,5-triazineFollowing the procedure of Example 4, Part B, 2-amino-4-butyl-6-diallylamino-1,3,5-triazine (6.2 g.; 0.025 mole) wasoxidized with m-chloroperbenzoic acid (95% pure; 9.0 g.; 0.05 mole).There was obtained 1.05 g. of1,Z-dihydro-1-hydroxy-6-butyl-4-diallylamino-Z-imino- 1,3,5-tn'azine inthe form of a white solid which gave a positive ferric chloride test;M.P. 82-85 C.

AnalysiS.-Calcd. for C13H21N5OZ C, H, 8.04. Found: C, 58.97; H,7.57.U.V.(C H OH) 212 m (=26,450); 258 m (e=16,100); 308 m (e=6,000).I.R.(Principal bands; mineral oil mull) 3340, 3070, 164 0, 1585, 1525,1260, 1152, 1109, 1006 cmr EXAMPLE 10 PartA.-2-dimethylamino-4-octyl-6-propylamino- 1,3,5-triazine Following theprocedure of Example 8, Part A, 1,1- dimethyl-S-propylbiguanidehydrochloride is reacted with ethyl nonanoate in the presence of sodiumethoxide and ethanol to give 2-dimethyl-amino-4-octyl-6-propylamino-1,3,5-triazine.-

Part B.-1,2-dihydr0-1-hydroxy-4-dimethylamino-6-0ctyl-2-pr0pyl-imino-1,3,5-triazine Following the procedure of Example4, Part B, 2- dirnethylamino-4-octyl 6-propylamino 1,3,5-triazine isoxidized with rn-chloroperbenzoic acid to give 1,2-dihydro-1-hydroxy-4dimethylamino-6-octyl-2-propylamino-l,3,5-triazine.

EXAMPLE 11 Part A.--2-amin0-4-cycl0l1exyl-6-diallylamin0-1,3,5-

triazine Following the procedure of Example 8, Part A,1,1-diallylbiguanide hydrochloride (43.5 g.; 0.20 mole) was reacted withmethyl cyclohexanecarboxylate (31.0 g.; 0.22 mole) in the presence ofsodium ethoxide and ethanol. A 48-hour reaction time was used. Theproduct was recrystallized from a mixture of methanol and water to give31.9 g. of 2-amino-4-cyclohexyl-6-diallylamino- 1,3,5-triazine in theform of colorless needles; M.P. 92 C.

Analysis.Calcd. for C H N C, 65.90; H, 8.48; N, 25.62. Found: C, 66.31;H, 8.44; N, 25.15. U.V. (C H OH) 231 m (sh.) (e=2,000); 262 m (e=503).I.R.(Principal bands; mineral oil mull) 3320, 3105, 1660, 1646,1585-1490 (broad band), 1245, 1215, 1188, 1070 cm.-

Part B.-1,2-diIzydr0-1 -hydr0xy-6-cyclohexyl-4-diallylamin0-2-imin0-1,3,5-triazine Following the procedure of Example4, Part B, Z-amino- 4-cyclohexyl-6-diallylamino-1,3,5-triazine (6.8 g.;0.025 mole) was oxidized with m-chloroperbenzoic acid (95 pure; 9.0 g.;0.05 mole). The oil which precipitated from the aqueous alkalinesolution and the residue which remained after evaporation of thecombined chloroform extracts were combined and recrystallized fromacetonitrile to give 1.9 g. of 1,2-dihydro-1-hydroxy-6-cyclohexyl-4-diallylamino-2-imino-1,3,5-triazine in the form of colorless needles;M.P. 139-142 C.

Analysis.Calcd. for C H N O: C, 62.26; H, 8.01; N, 24.20. Found: C,62.56; H, 7.74; N, 23.85. U.V. (H 0) 255 m (e=16,300); 305 m (e=5,600).(0.01 N H01) 226 mu (e=18,500); 240 m (sh.) (e=16,050); 260 mu(e=7,750). (0.01 N KOH) 255 mu (e=16,300); 305 m (e=5,650).I.R.(Principal bands; mineral oil mull) 3355, 3080, 1666, 1643, 1565,1530, 1257, 1182, 1149, 1136 cmf EXAMPLE 12 Part A.2-amino-4-diallylamin0-6-phenyl-I ,3,5- triazz'ne Sodium metal (9.2 g.;0.40 gram atom) was reacted with 200 ml. of methanol, and the mixturewas added to a stirred solution of 1,1-diallylbiguanide hydrochloride(43.5 g.; 0.20 mole) in ml. of methanol at about 25 C. Methyl benzoate(29.9 g.; 0.22 mole) was then added to the resulting stirred mixture at25 C. After stirring for 53 hours at 25 C., the reaction mixture wasdiluted to 2000 ml. with water. The precipitate which formed wasfiltered and recrystallized from methanol to give 25.6 g. of2-amino-4-diallylamino-6-phenyl-1,3,5-triazine in the form of whitecrystals; M.P. 8284 C. Addition of about 1000 ml. of water to thefiltrate gave an additional 6.2 g. of the same product.

Analysis.Calcd. for C H N C, 67.39; H, 6.41; N, 26.20. Found: C, 67.12;H, 6.39; N, 25.71. U.V.- (C H OH) 220 my. (sh.) (e=23,100); 242 my.(e=32,600); 281 my. (sh.) (e=5,150); 298 mp (sh.) (e:=3,000).'I.R.(Principal bands; mineral oil m-ull) 3325, 3165, 1650, 1589, 1545,1525, 1246, 1179, 1165, 778, 705 cm.-

Part B.I,2-dihydr-1-hydroxy-4-diallyIamin0-2-imino-6-pinenyl-1,3,5-triazine Following the procedure of Example 4,Part B, 2-amino- 4-diallylamino-6-phenyl-1,3,5-triazine (6.7 g.; 0.025mole) was oxidized with m-chloroperbenzoic acid (95% pure; 9.0 g.; 0.05mole). The oil which separated from the aqueous alkaline solution andthe solid residue remaining after evaporation of the combined chloroformextracts were combined and recrystallized from a mixture of we tonitrileand diethyl ether to give 0.4 g. of1,2-dihydro-lhydroxy-4-diallylamino-2-imino-6-phenyl-1,3,5-triazine inthe form of yellow crystals which gave a dark brown ferric chloridetest; M.P, 135-145 C.

Analysis.Calcd. for C H N O: C, 63.58; H, 6.05; N, 24.72. Found: C,63.60; H, 5.56; N, 24.31. U.V. (C H OH) 259 m (e=27,300); 345 mg(e=3,'600). I.R.-(Principal bands; mineral oil mull) 3315, 1665, 1585,1566, 1551, 1488, 1210, 1126, 765, 690 cmr EXAMPLE 131,Z-dihydro-I-hydroxy-4-dimethylamin0-2-imino-6- phenyl-1,3,5-triazineFollowing the procedure of Example 4, Part B, 2-amino-4-dimethylamino-S-phenyl-1,3,5-triazine is oxidized withm-chloroperbenzoic acid to give 1,2-dihydro-1-hydroxy-4-dimethylamino-2-imino-6-phenyl-1,3,5-triazine,

EXAMPLE 14 Part A .--1-allyl-1-methylbiguanide hydrochloride Followingthe procedure of Shapiro et al., I. Am. Chem. Soc. 81, 3728-36 (1959),N-methylallylamine hydrochloride is fused with cyanoguanidine to givel-allyl-lmethylbiguanide hydrochloride.

Part B.2-amino-4-(N-methylallylamino) -6-p-t0lyl- 1,3,5-triazineFollowing the procedure of Example 12, Part A, l-allyll-methylbiguanidehydrochloride is reacted with methyl p-toluate in the presence of sodiummethoxide and methanol to give 2-amino-4-(N-methylallylamino)-6-p-tolyl-1,3,5-triazine.

Part C.1,Z-dihydro-I-hydroxy-2-imin0-4-(N-methylallylamino)-6-p-t0lyl-1,3,5-triazine Following the procedure of Example 4, Part B,Z-amino- 4(N-methylallylamino)-6-p-to1yl-1,3,5-triazine is oxidized withm-chloroperbenzoic acid to give 1,2-dihydro-1-hydroxy-2-imino4-(N-methylallylamino) -6-p-tolyl-1,3,5- triazine.

EXAMPLE 15 Part A.2-amin0-4-diallylamino6-(2-methoxyethyl)-1,3,5-triazine Sodium metal (13.8 g.; 0.60 gram atom) was reacted with300 ml. of methanol, and the mixture was added to a stirred solution of1,1-diallylbiguanide hydrochloride (65.3 g.; 0.30 mole) in 200 ml. ofmethanol at about 25 18 C. Methyl acrylate (30.1 g.; 0.35 mole) was thenadded to the resulting stirred mixture at 25 C. After stirring for 72hours at 25 C., the reaction mixture was diluted to 2000 ml. with water.The oil which separated did not crystallize, and was extracted with five200-ml. portions of methylene chloride. The combined extracts werewashed with water, dried, and evaporated to give an oily residue whichwas distilled at reduced pressure to give 47.0 g. of2-amino-4-diallylamino-6-(Z-methox'yethyl) 1,3,5-triazine in the form ofacolorless viscous oil; B.P. 144l60 C. at 0.2 to 0.7 mm.

Analysis.Calcd. for C H N O: C, 57.81; H, 7.68; N, 28.09. Found: C,57.73; H, 7.80; N, 27.81. U.V. (C H OH); 264 my. (c=4,670); 212 mp.(e=25,320); 220 my (sh.) (e=23,840); 228 my (sh.) (e=21,720); 236 my.(sh.) (e=l6,320). I.R.(Principal bands; no diluent) 3323, 3200, 3150,3080, 1640, 1565, 1535, 1515, 1195, 1155, 1090 GEL-1.

Part B.1,Z-dihydro-I-hydroxy-4-diallylamino-Z-imina-6-(2-methaxyethyl)-1,3,5-triazine Finely-divided m-chloroperbenzoic acid(91.5% pure; 11.3 g.; 0.06 mole) was added gradually during 20 minutesto a stirred solution of 2-amino-4-diallylamino-6-(2-methoxyethyl)-l,3,5-triazine (7.5 g.; 0.03 mole) in 350 ml. of absoluteethanol at 5 C. The resulting reaction mixture was stirred 8 hours at0-5 C. and 15 hours while rising gradually to 25 C. At this point, astarchiodide test forperacids was negative. Solvent was removed atreduced pressure to give a white solid to which was added a solution of10 ml. of concentrated hydrochloric acid in 200 ml. of water. Thismixture was filtered. The filter cake was washed with water, and thecombined filtrate and washings were adjusted to pH 9 with aqueous sodiumhydroxide solution. The yellow oil which formed was allowed to settlefor 4 hours. The alkaline aqueous layer was decanted and extractedrepeatedly with chloroform until a portion of a fresh extract did notgive a dark color to ethanolic ferric chloride. The combined extractswere dried with sodium sulfate and evaporated to give a yellow oil whichwas crystallized from acetonitrile to give 3.75 g. of1,2-dihydro-1-hydroxy- 4-diallylamino-2-imino-6-(Z-methoxyethyl)-1,3,5triazine in the form of a light-yellow solid which gave a dark browncolor to ethanolic ferric chloride; M.P. 132- 134 C.

Analysis.Calcd. .for C H N O C, 54.32; H, 7.22; N, 26.40; 0, 12.06.Found: C, 54.32; H, 6.80; N, 26.06; 0, 12.43. U.V.(H O) 211 m(e=24,050); 255 m (e=16,050); 306 m (6:5,600). (0.01 N H SO 227 m(e=18,450); 242 m (sh.) (e=l5,200); 272 mu (sh.) (6=5,800). (0.01 NNaOH) 255 m (e=16,300); 306 m (e=5,700). I.R.(Principal bands; materialoil mull) 3340, 2660, 1565, 1525, 1475, 1190, 1110, 1040, 775, 730, 705cm.-

Addition of absolute ethanol containing one equivalent of hydrogenchloride to an absolute ethanol solution of1,Z-dihydro-1-hydroxy-4-diallylamino-2 imino 6 (2-methoxyethyl)-1,3,5-triazine followed by addition of about 4 volumes ofdiethyl ether gives the triazine monohydrochloride. Use of 2 equivalentsof hydrogen chloride in this procedure gives the dihydroehloride.Similar use of one molecular amount of lactic acid gives the monolacticacid addition salt.

EXAMPLE 16 Part A.-2-amino-4-diallylamino-6-(2-methoxypropyl)1,3,5-triazine Following the procedure of Example 15, Part A, 1,1-diallylbiguanide hydrochloride (43.5 g.; 0.20 mole) was reacted withmethyl crotonate (22.0 g.; 0.22 mole) in the presence of sodiummethoxide and methanol. Distillation of the product gave 34.8 g. of2-amino-4-diallylamino- 6-(2-methoxypropyl)-1,3,5-triazine in the formof a colorless viscous oil; B.P. -l47 C. at 0.25 to 0.40 mm.

19 Analysis.Calcd. for C H N O: C, 59.29; H, 8.04; N, 26.60. Found: C,59.36; H, 8.42; N, 26.17. U.V.- 1-1 011) 214 my $26,300 226 my (sh.)(e=23,900); 264 my (e=4,550). LR. (Principal hands; no diluent) 3323,3200, 3150, 3080, 1640, 1565, 1535, 1515, 1195, 1155, 1090 cmr PartB.--1,Z-dihydro-I-hydroxy-4-diallylamino-2-imin0- 6-(Z-methoxypropyl)-1,3,5-triazine Following the procedure of Example 15,Part B, 2- amino-4-diallylamino-6-(Z-methoxypropyl) -1,3,5 triazine(10.5 g.; 0.04 mole) was oxidized with m-chloroperbenzoic acid (91.5%pure; 15.1 g.; 0.08 mole) to give 1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6 (2methoxypropyl)-1,3,5-triazine in the form of an oil which gave apositive ferric chloride test and which did not crystallize.

U.V. (H O) 211.5 m (e=23,800); 255 my (e=14,450); 307 m (5:4,450). (0.01N H SO 227 m (e=18,600); 244 my (sh.) (e=14,700); 270 m (sh.) (e=5,750).(0.01 N KOH) 255 m (e=14,500); 306 my (6=4,550). I.R.-(Prin-cipal hands;no diluent) 3300, 3070, 1648, 1585, 1530, 1483, 1175, 1155, 1085 cm.-

EXAMPLE 17 Part A.2-amin0-4-diaIlylamin0-6-vinyl-1,3,5-triazine Sodiummetal (9.2 g.; 0.40 gram atom) was reacted with 500 ml. of ethyleneglycol monomethyl ether. To this mixture was added 1,1-diallylbiguanidehydrochloride (87.0 g.; 0.40 mole). The sodium chloride whichprecipitated was filtered. Methyl acrylate (34.4 g.; 0.40 mole) wasadded with stirring to this filtrate at 25 C. After stirring for anadditional 63 hours at 25 C., the reaction mixture was concentrated atreduced pressure to about one-half its original volume and was thendiluted with ice-water to 2000 ml. The oil which separated was extractedwith four 250-ml. portions of methylene chloride, and the combinedextracts were dried with sodium sulfate and evaporated. The oily residuewas distilled at reduced pressure. The fraction which distilled at 138to 168 C. at 0.45 to 1.0 mm. was collected separately. This fractionsolidified and was recrystallized from a mixture of methanol and waterto give 14.9 g. of 2-amino-4-diallylamino-6-vinyl-1,3,5-triazine in theform of a white solid; M.P. 64-65 C.

Analysis.Ca'lcd. for C H N C, 60.80; H, 6.96. Found: C, 60.50; H, 6.59.U.V.(C H OH) 215 m (e=37,250); 226 my (sh.) (e=34,250); 290 my.(e=2,900). I.R.(Principal bands; mineral oil mull) 3310, 3130, 1666,1649, 1530, 1238 cm.'-

Part B.1,2-dihydr0-1-hydr0xy-4-diallylamino-2-imin0-6-vinyl-1,3,5-triazine Following the procedure of Example 15, Part B, 2-amino-4-diallylamino-6-vinyl-1,3,5-triazine (8.7 g.; 0.04 mole) wasoxidized with m-chloroperbenzoic acid (91.5 pure; 15.1 g.; 0.08 mole).The oil which separated from the alkaline aqueous solution and the oilremaining after evaporation of the combined chloroform extracts werecombined and adsorbed on a column of Florisil (60-100 mesh; a magnesiumtrisilicate; obtained from the Floridin Company, Warren, Pa.). Afterchloroform elution of 0.85 g. of starting triazine, elution with amixture of equal volumes of methanol and chloroform followed byevaporation of the eluate gave 4.5 g. of 1,2-dihydro-l-hydroxy-4-diallylamino-2-imino-6-vinyl-1,3,5-triazine in the form of a viscousyellow oil which gave a dark brown color to alcoholic ferric chlorideand which did not crystallize.

U.V.-(H O) 208 my (end absorption); 253 my (=6,550); 306my (e=1,850).(0.01 N H 80 227 m (s=10,l00); 240 m (sh.) (e=8,450); 268 m (sh.)(e=2,700). (0.01 N KOH) 254 m (e=6,300); 307 my (c=l,700).I.R.(Principa1 bands; no diluent) 3320,

EXAMPLE 18 Part A .-2-allyl-4-amin0-6- (Z-methylpiperidino) -I,3,5-triazine Following the procedure of Example 17, Part A, 1,1-(1-methylpentamethylene)biguanide hydrochloride is reacted with methyl3-lbutenoate to give 2-ally1-4-amino-6-(2-methylpiperidino)-l,3,5-triazine.

Part B.1,2-dihydro-1-hydr0xy-6-allyl-2-imin0-4-(2-methylpiperidino)-1,3,5-triazine Following the procedure of Example 15, Part B, 2-allyl-4-amino-6-(Z-methylpiperidino)-1,3,5-triazine is oxidized withm-chloroperbenzoic acid to give 1,2-dihydro-l-hydroxy 6-ally12-imino-4-(2-methylpiperidino)-l,3,5-triazine.

EXAMPLE 19 Part A.-2-amin0-4-diallylamino-6-propyl-1,3,5-triazine Sodiummetal (9.2 g.; 0.40 gram atom) was reacted with 200 ml. of methanol, andthe mixture was added to a stirred solution of 1,1-diallylbiguanidehydrochloride (43.5 g.; 0.20 mole) in ml. of methanol at about 25 C.Methyl butyrate (22.5 g.; 0.22 mole) was then added to the resultingstirred mixture at 25 C. After stirring for 69 hours at 25 C., thereaction mixture was poured into 1500 ml. of water at 0 C. The solidwhich precipitated was filtered and recrystallized from a mixture ofmethanol and water to give 33.2 g. of2-amino-4-diallylamino-6-propyl-l,3,5-triazine in the form of whitecrystals; M.P. 50-52 C.

Analysis.Calcd. for C H N C, 61.77; H, 8.21; N, 30.02. Found: C, 62.17;H, 8.16; N, 29.74. U.V.- (C H OH) 212 m (e=26,150); 226 m (sh.) (is:21,950); 262 m (e=4,950). LR.-(Principal bands; mineral oil mull) 3320,3150, 1646, 1525, 1245, 1200 cm.''.

Part B.] ,Z-dihydro-I -hydr0xy-4-dialIylamino-2-imino-6-propyl-1,3,5-triazine Following the procedure of Example 15, Part B, 2-amino-4-diallylamino-6-propyl-1,3,5-triazine (9.3 g.; 0.04 mole) wasoxidized with m-chloroperbenzoic acid (91.5% .pure; 15.1 g.; 0.08 mole).The oil which separated from the aqueous alkaline solution and thematerial which remained after evaporation of the combined chloroformextracts were combined and crystallized from acetonitrile to give 2.8 g.of 1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6-propyl-1,3,5-tria.zine in the form of a white solid which gave adark brown color to ethanolic ferric chloride; M.P. 88-91 C.

Analysis.-Calcd. for C H N O: C, 57.81; H, 7.68; N, 28.09. Found: C,57.87; H, 7.74; N, 27.95. U.V.- (H 0) 210 m (e=23,950); 255 m (=14,650);305 m (5:4,800). (0.01 N H SO 226 m (e=18,150); 238 m (sh.) (e=15,700);274 m (sh.) (5:5,100). (0.01 N KOH) 255 m .14,600); 303 m (e=4,700).I.R.-(Principal bands; mineral oil mull) 3340, 3060, 1655, 1640, 1585,1525, 1175, 1155 cmr EXAMPLE 20 Part A.2-amin0-4-diallylamin0-6-is0pr0pyl-1,3,5-triazine Following theprocedure of Example 19, Part A, 1,1- diallylbiguanide hydrochloride(43.5 g.; 0.20 mole) was reacted with methyl isobutyrate (22.5 g.; 0.22mole). A 46-hour reaction time at 25 C. was used. The reaction productwas recrystallized from a mixture of ethanol and water to give 26.4 g.of 2-amino-4-diallylamino-6-isopropyl-1,3,5-triazine in the form of awhite solid; M.P. 49- 51 C.

Analysis.-Calcd. for C H N C, 61.77; H, 8.21; N, 30.02. Found: C, 62.32;H, 8.20; N, 29.56. U.V.- (C H OH) 212 my (=26,000); 230 my (sh.) (e:

21 20,050); 257 m (e=5,050). I.R.(Principal bands; mineral oil mull)3320, 3150, 1646, 1525, 1245, 1200, 825, 695 cm.**.

Part B.1,2-dihydr-I-hydr0xy-4-diallylamino-2-imino-6- isopropy l-] ,3 ,5triazine Following the procedure of Example 15, Part B, 2-amino-4-diallylamino-6-isopropyl-l,3,5-triazine (9.3 g.; 0.04 mole) wasoxidized with m-chloroperbenzoic acid (46% pure; 30.0 g.; 0.08 mole).The reaction product was recrystallized twice from acetonitrile to give1.2 g. of1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6-isopropy1-l,3,5-t-riazinein the form of white crystals which gave a positive ferric chloridetest; M.P. '119-121 C.

Analysis.-Calcd. for C l-1 N 02 C, 57.81; H, 7.68; N, 28.09. Found: C,58.13; H, 7.78; N, 27.41. U.V.-- (H 0) 210 my. (end absorption); 255 m(e=16,400); 303 m (e=5,600). (0.01 N H SO 226 m (8: 18,000); 239 m(e=16,050); 272 mu (sh.) (e=6,000). (0.01 N KOH) 255 m (e=16,400); 304 m(=5,700). I.-R.(Principal bands; mineral oil mull) 3340, 3075, 1690,1662, 1642, 1583, 1530, 1255, 1152 cmr EXAMPLE 21 PartA.2-amin0-4-diallylamin0-6-pentyl-1,3,5-triazine Following the procedureof Example 19, Part A, 1,1- diallylbiguanide hydrochloride (43.5 g.;0.20 mole) was reacted with ethyl hexanoate (31.7 g.; 0.22 mole). A70-hour reaction time was used. When the reaction mixture was pouredinto water, the product separated as an oil which did not crystallize.This oil was extracted with 1000 ml. of methylene chloride in severalportions. The combined extracts were dried with sodium sulfate.Evaporation of the solvent gave a viscous residue which was distilledunder reduced pressure to give 35.3 g. of2-amino-4-diallylamino-6-pentyl-1,3,5-triazine in the form of acolorless viscous oil; B.-P. 155-157 C. at 1 Analysis.-Calcd. for C H NC, 64.33; H, 8.87; N, 26.80. Found: C, 63.78; H, 8.82; N, 26.32. U.V. (CH OH) 212 my. (e=25,800); 224 m (sh.) (6: 22,350); 263 my. (6=5,000).I.R.-(Principal hands; no diluent) 3480, 3320, 3200, 3150, 3080, 1660,1640, 1575, 1550, 1525, 1245, 1195, 1115, 1050 cm.-

Part B.I,2-dihydro-1-hydr0xy-4-diallylamin0-2-imino-6-pentyl-1,3,5-triazine Following the procedure of Example 15, Part B, 2-amino-4-diallylamino-6-pentyl-1,3,5-triazine (10.45 g.; 0.04 mole) wasoxidized with m-chloroperbenzoic acid (91.5% pure; 15.1 g.; 0.08 mole)in a mixture of 200 ml. of absolute ethanol and 100 ml. of methanol.There was obtained from the chloroform extracts, 1.3 g. of 1,2- dihydro1 hydroxy-4-diallylamino-2-imino-6-pentyl- 1,3,5-triazine in the form ofa yellow oil which gave a dark brown color to ethanolic ferric chlorideand which did not crystallize.

U.V.-(H O) 210 m (e=19,400); 254 m (e=9,150); 304 mp. (=2,700). (0.01 NH3804) 224 my. (e= 14,950); 237 m (e=12,800); 268 m (sh.) (e=4,250).(0.01 N KOH) 234 m (sh.) (e=8,950); 254 m (6: 8,900); 304 my. (e=2,600).

EXAMPLE 22 Part A.--2-amin0-4-p-chlorobenzyl-6-diallylamin0-1,3,5-triazine Sodium metal (11.5 g.; 0.50 gram atom) was reacted with 350 ml.of methanol, and the mixture was added rapidly to a stirred solution of1,1-diallyl-biguanide hydrochloride (50.5 g.; 0.25 mole) in 100 ml. ofmethanol at about 25 C. Methyl p-chlorophenylacetate (50.6 g.; 0.27mole) was then added to the resulting stirred mixture at 25 C. Afterstirring for 111 hours at 25 C., the reaction mixture was diluted to2000 ml. with .water.

The solid which precipitated rwas filtered and recrystallized from amixture of methanol and water to give 53.3 g. of 2-aminoi-p-chlorobenzyl-6-diallylamino-l,3,5-triazine in the form ofcolorless needles; M.P. 87-89 C.

Analysis.-Ca1cd. for C H ClN C, 60.85; H, 5.74; Cl, 11.23. Found: C,60.76; H, 5.62; Cl, 11.44. U.V.- (C H OH) 216 mn (e=34,250); 265 m(e=4,750); 276 my (sh.) (e=3,450). oil mull) 3470, 3330, 3130, 3100,1645, 1563, 1546, 1524, 1486, 1250, 1190, 1178, 1148, 1086, 1015, 754cmr PartB.1,2-dihydro-I-hydr0xy-6-p-chlor0benzyl-4-diallylamino-Z-imz'no-I,3,5-triazineFollowing the procedure of Example 15, Part B, 2-amino-4-p-chlorobenzyl-6-diallylamino-l,3,5-triazine (12.6 g.; 0.04mole) was oxidized with m-chloroperbenzoie acid (91.5% pure; 15.1 g.;0.08 mole) in a mixture of 300 ml. of absolute ethanol and 250 ml. ofmethanol. The initial white solid reaction product was treated fourtimes with a mixture of water and concentrated hydrochloric acid ratherthan only once, being filtered and .washed with water after eachtreatment. Each aqueous acidic filtrate was combined with thecorresponding washing and adjusted to pH 9 with aqueous sodium hydroxidesolution. In each case, the yellow oil which formed was allowed tosettle for four hours. Aqueous layers were decanted and each wasextracted repeatedly with chloroform. All chloroform extracts were driedand evaporated to give a residue which was combined with all otherportions of yellow oil, the whole being dissolved in about 30 ml. ofchloroform. This chloroform solution was dried and adsorbed on a columnof Florisil (60-100 mesh). After chloroform elution of unreactedstarting triazine, elution with a mixture of equal volumes of methanoland chloroform followed by evaporation of the eluate gave 4.45 g. of1,Z-dihydro-l-hydroxy-G-p-chlorobenzyl-4-diallylamino-2-imino-1,3,5-triazine in the form of an amorphous yellowsolid which did not crystallize from the usual crystallization solvents;M.P. 65-80" C.

U.V.-(C H OH) 211 m (sh.) (e=31,850); 259 m (e=12,200); 313 m (e=3,950).(0.01 N ethanolic H 80 228 m (sh.) (e=21,150); 248 m (sh.) (a: 11,800);270 m (sh.) (e=5,950). (0.01 N ethanolic KOH) 260 mu (e=1-l,800); 313 mu(e=3,950). I.R.- (Principal bands; mineral oil mull) 3460, 3300, 3065,

1655, 1645, 1575, 1485, 1255, 1087, 1014, 752 cmf EXAMPLE 23 Part A.2-amin0-4-p-methylbenzyl-6-(I-pyrrolidinyl 1 ,3 ,5 -triazine Followingthe procedure of Example 22, Part A, 1,1- tetramethylenebiguanidehydrochloride is reacted with methyl p-methylphenylacetate in thepresence of sodium methodixe and methanol to give2-amino-4-p-methylbenzyl-6-( 1-pyrrolidinyl)-1,3,5-triazine.

- PartB.1,Z-dihydro-I-hydr0xy-2-imin0-6-p-methylbenzyl-4-(1-pyrrolidinyl),3,5-triazine Following the procedure of Example 15, Part B, 2- amino4-p-methy1benzyl-6-( 1-pyrrolidinyl)-1,3,5 -triazine is oxidized withm-chloroperbenzoic acid to give 1,2-dihydro 1 hydroxy-Z-imino-6-p-methylbenzyl-4-(l-pyrrolidinyl)-1,3,5-triazine.

EXAMPLE 24 Part A .-2-amino-4-(1 -hexahydr0azepinyl)-6-p-methoxybenzyl-1,3,5-triazine I.R.(Principal bands; mineral 23 PartB.1,2-dilzydro-1-hydr0xy-4-(l-hexalzydroazepinyl)-2-imirm-6-p-meth0xybenzyl-1 ,3,5-triazine Following the procedure ofExample 15, Part B, 2- amino 4 (l-hexahydroazepinyl)-6-p-methoxybenzyl)-1,3,5-triazine is oxidized with m-chloroper-benzoic acid to give 1,2dihydro-l-hydroxy-4-('l-hexahydroazepinyl)-2-imino-6-p-methoxybenzyl-1,3,5-triazine.

EXAMPLE 25 Part A .2-amino-4-diallylamino-6-phenethyl-],3,5-

triazz'ne Following the procedure of Example 19, Part A, 1,1-diallylbiguanide hydrochloride (43.5 g.; 0.20 mole) was reacted withmethyl 3-phenylpropionate (36.1 g.; 0.22 mole). A 45-hour reaction timewas used. The oil which formed when the reaction mixture was poured intowater did not crystallize and was extracted with four 250-ml. portionsof methylene chloride. The combined extracts were dried with sodiumsulfate and evaporated to give a viscous residue which was distilledunder reduced pressure to give 37.8 g. of 2-amino-4-diallylamino-6-phenethyl-1,3,5-triazine in the form of a viscous liquid; B.P. 180-182"C. at 0.3 mm.

Analysis.Calcd. for C H N C, 69.12; H, 7.17; N, 23.71. Found: C, 69.13;H, 6.90; N, 23.30. U.V.- 11 011) 210 m, ($34,550 228 m (sh.) (6: 22,750)262 m (e=4,900). I.R.-(Principal hands; no diluent) 3470, 3320, 3150,3080, 3050, 1650, 1545, 1236, 810, 690 cmr- PartB.-J,2-dihydr0-1-hydroxy-4-diallylanzino-Z-imino-6-phenethyI-1,3,5-triazirze Finely divided m-chloroperbenzoic acid(91.5% pure; 15.1 g.; 0.08 mole) was added gradually during minutes to astirred solution of 2-amino-4-diallylamino-6- phenethyl-1,3,5-triazine(11.8 g.; 0.04 mole) in 150 ml. of absolute ethanol at 5 C. Theresulting reaction mixture was stirred 7 hours at 0-5 C. Solvent wasthen removed at reduced pressure and 100 ml. of water was added to theresidue. The mixture was made alkaline with aqueous sodium hydroxidesolution and extracted with five 50-ml. portions of chloroform. Thecombined extracts were dried with sodium sulfate and evaporated.Trituration of the residue with acetonitrile produced a solid which wasrecrystallized from acetonitrile to give 6.15 g. of1,2-dihydro-1-hydroxy-4-diallylamino-Z-imino-6-phenethyl 1,3,5- triazinein the form of white needles which gave a dark brown color to ethanolicferric chloride; M.P. 118-120" C.

AnaIysis.-Calcd. for C H N O: C, 65.57; H, 6.80; N, 22.49. Found: C,65.86; H, 6.53; N, 22.27. U.V. (H 0) 209 mu (end absorption); 256 m,(e=16,150); 306 my (e=5,450). (0.01 N H 50 224 mu (sh.) (s=30,350); 250m (e=18,300); 262 m (sh.) (6: 15,500). (0.01 N KOH) 256 my (e=16,050);306 mu (e=5,400). I.R.(Principal bands; mineral oil mull) 3400, 3270,3070, 3020, 1665, 1640, 1580, 1525, 1485, 1263, 1182, 768, 690 cmi- Asolution of 1,2-dihydro-1-hydroxy-4-diallylamino-Z-imino-6-phenethyl-1,3,5-triazine in water containing one equivalent ofhydrochloric acid (about 1% hydrochloric acid) gives themonohydrochloride when evaporated to dryness. Similar use of 2equivalents of hydrochloric acid gives the dihydrochloride. Similar useof one molecular amount of sulfuric acid gives the monosulfuric acidaddition salt.

EXAMPLE 26 Part A .2-amino-4-diallylamino-6-(S-phenylpropyl )-1,3,5-zriazine Following the procedure of Example 19, Part A, 1,1-diallylbiguanide (43.5 g.; 0.20 mole) was reacted with methyl4-phenylbutyrate (39.2 g.; 0.22 mole). A 48-hour reaction time was used.The reaction product was recrystallized from hexane to give two crops(16.85 g. total) of 2amino-4-diallylamino-6-(3-phenylpropyl)-1,3,5-triazine in the form ofyellow crystals; M.P. 5760 C.

Analysis.-Calcd. for C H N C, 69.87; H, 7.49; N, 22.64. Found: C, 69.82;H, 7.41; N, 22.02. U.V.- (C H OH) 209 m (e=33,600); 228 mu (sh.) (6:21,850); 260 mu (e=5,400). I.R.-(Principal bands; mineral oil mull)3305, 3100, 3010, 1655, 1525, 1243, 735, 693 cmr PartB.],2-dihydr0-1-hydroxy-4-dially[amino-Z-imino-6-(3-phenylpr0pyl)-1,3,5-triazine Following the procedure of Example 25,Part B, 2- amino-4-diallylamino-6-(3-phenylpropyl) 1,3,5 triazine (10.15g.; 0.033 mole) was oxidized with m-chloroperbenzoic acid (91.5% pure;12.4 g.; 0.066 mole). The reaction mixture was stirred for an additional60 hours at 25 C. The reaction product was an oil which did notcrystallize. The oil was dissolved in chloroform and adsorbed on acolumn of Florisil (60100 mesh). After elution of 1.4 g. of unreactedstarting triazine with 100 ml. of chloroform, further elution first with3000 ml. of chloreform and then with 500 ml. of chloroform containing20% by volume of methanol gave eluates which were combined andevaporated. The resulting residue was recrystallized twice fromacetonitrile to give 3.2 g. of 1,2- dihydro 1 hydroxy 4 diallylamin-o 2imino 6- (3-phenylpropyl)1,3,5-triazine in the form of a white solidwhich gave a dark brown color to ethanolic ferric chloride; M.P. 91-93C.

AnaIysis.Calcd. for C H N O: N, 21.52. Found: N, 21.08. U.V.(HgO) 255 mu(E=15,250); 305 mu (e=5,250). (0.01 N H 226 mp. (e=17,800); 240 my.(sh.) (e=l5,200); 274 m (sh.) (c=5,300). (0.01 N NaOH) 251 mu(e=14,850); 301 my. (e=4,900). I.R.-(Principal bands; mineral oil mull)3330, 3050, 1660, 1640, 1583, 1515, 1167, 763, 685 cm.

EXAMPLE 27 Part A.--2-amin0-4-cycl0pr0pyI-6-diallylamino- 1,3,5-triazineFollowing the procedure of Example 19, Part A, 1,1-diallylbiguanidehydrochloride (52.2 g.; 0.24 mole) was reacted with methylcyclopropanecarboxylate (26.0 g.; 0.26 mole). A 42-hour reaction timewas used. The reaction product was recrystallized from a mixture ofethanol and water to give 26.2 g. of2-amino-4-cyclopropyl-6-diallylamino-1,3,5-triazine in the form of awhite solid; M.P. 55-57.5 C.

Analysis.Calcd. for C H N C, 62.31; H, 7.41; N, 30.28. Found: C, 62.03;H, 7.21; N, 29.70. U.V. (C H OH) 206 my (end absorption); 224 m (sh.)(6: 24,150); 262 m (e=4,400). I.R.-(Principal bands; mineral oil mull)3320, 3130, 3080, 1660, 1640, 1540,

Part B.I,2-dihydr0-1-hydroxy-6-cyclopr0pyI-4-diallylamino-Z-imino-I,3,5-triazine Following the procedure of Example25, Part B, 2- amino-4-cyclopropyl-6-diallylamino-1,3,5 triazine (9.25g.; 0.04 mole) was oxidized with m-chloroperbenzoic acid (54% pure; 25.5g.; 0.08 mole) in 250 ml. of absolute ethanol. After a 7-hour reactionperiod at 0-5 C., sodium methoxide (4.05 g.; 0.075 mole) was added andthe reaction mixture was stirred for an additional 15 hours at 25 C.Solvent was then removed at reduced pressure and m1. of water was addedto the residue. Solid unreacted starting triazine (5.45 g.) was removedby filtration, and the filtrate was extracted with chloroform as inExample 25, Part B. The residue obtained by evaporation of the combinedchloroform extracts was recrystallized four times from acetonitrile togive 06 g. of 1,2- dihydro 1 hydroxy 6 cyclopropyl 4 diallylamino-2-imino-l,3,5-triazine in the form of a white solid which gave apositive ferric chloride test; M.P. 104-106 C. (sintered at 102 C.).

Analysis.Calcd. for C H N O: -N, 28.32. Found: N, 28.14. U.V.(H O) 253 m(e=11,400); 304 mn (=3,000). (0.01 -N H S 227 m '(e=23,400); 240 mp.(sh.) (e=19,200); 270 m (sh.) (e=5,550). (0.01 N KOH) 2541111.!-(e=11,400); 305 my. (e=3,000). LR.- (Principal "bands; mineral oil mull)3285, 3240, 3195, 3080, 3010, 1675, 1650, 1588, 1545, 1530, 1242, 1190,1115 cm.'-

Following the procedure of Example 1, Part B; Example 5, Part B; Example15, Part B; or Example 25, Part B, the monoand diacid addition salts of1,2-dihydro-l-hydroxy 6 cyclopropyl 4diallylamino-Z-imino-l,3,5-triazine with hydrochloric acid, sulfuricacid, phosphoric acid, lactic acid, benzoic acid, and succinic acid areprepared.

EXAMPLE 28 Part A.2-allylamino-4-chl0r0-6-methyl-1,3,5-triazineAnalysis.Calcd. for C H C1N Cl, 16.42; N, 30.35.

Found: Cl, 16.42; N, 30.58. U.V.--(C H OH) 232 m (e=20,800); 264 mp.(sh.) (e=2,150). I.R.(Principal bands; mineral oil mull) 3270, 3120,1650, 1612, 1565, 1535, 1-275, 1175, 1141 cmr PartB.-2-allylamino-4-diaIlylamin0-6-methyl-1,3,5-

triazine Asolution of diallylamine (9.7 g.; 0.10 mole) in 50 ml. ofdimethylformamide was added to a solution of2-allylamino-4-chloro-6-methyl-l,3,5-triazine (9.2 g.; 0.05 mole) in 50ml. of dimethylformamide at about 25 C. The mixture was heated at 100 C.for 2 hours, and was then cooled to about 30 C. and diluted to 500 ml.with water. The solid which precipitated was filtered, and was twicedissolved in ethanol and precipitated with water to give 9.0 g. of2-allylamino-4-diallylamino-6-methyl-1,3,5-triazine; M.P. 40-41.5 C.

Analysis.-Calcd. for C H, N C, 63.64; H, 7.81; N, 28.55. Found: C,64.29; H, 7.40; N, 28.26. U.V.-- (C H 0H) 225 m (e=35,700); 266 m(e=5,100). I.R.-(Principal bands; mineral oil mull) 3460, 3270, 3140,3095, 1642, 1605, 1585, 1538, 1515, 1500, 1226 cm.-

PartC.1,2-dihydra-1-hydroxy-2-allylimin0-4-diallylamin0-6-methyl-1,3,5-triazineFollowing the procedure of Example 25, Part B,2-allylamino-4-diallylamino-6-methyl-1,3,5-triazine (6.1 g.; 0.025 mole)was oxidized with rn-chloroperbenzoic acid (91.5% pure; 9.4 g.; 0.05mole) in 100 ml. of absolute ethanol. The reaction mixture was stirredfor an additional 15 hours at 25 C. The reaction product wasrecrystallized twice from hexane to give 3.3 g. of1,2-dihydro-l-hydroxy-2-allylimino-4-diallylamino-6-methyl-l,3,5-triazine in the form of awhite solid which gave a reddish-brown color to ethanolic ferricchloride; M.P. 7880 C. (sintered at 72 C.).

.Analysis.Calcd. for C H N O: C, 59.75; H, 7.33; N, 26.80; 0, 6.12.Found: C, 60.08; H, 7.25; N, 26.01; 0, 5.98. U.V.--(H O) 223 m(e=24,500); 255 m (E=15,900); 301 m (e=6,150). (0.01 N H 80 215 m(e=21,500); 228 m (e=23,300); 248 mu (sh.) (e=15,600); 272 mu (sh.)(e=6,600). (0.01 N KOH) 223 mu (e=24,500); 255 11111. (c=15,750); 301 m(e=6.050). I.R.( Principal bands; mineral oil mull) 3140, 3080, 1630,1590, 1530, 1267, 1185, 1127 cmr 26 EXAMPLE 29 PartA.2-anilin0-4-chloro-6-methyl-1,3,5-triazine Following the procedure ofExample 28, Part A, 2,4- dichloro-6-methyl-1,3,5-triazine (16.4 g.; 0.10mole) was reacted with aniline (18.6 g.; 0.20 mole) in 300 ml. ofdiethyl ether. There was obtained 23.4 g. of 2-anilino-4-chloro-6-methyl-l,3,5-triazine in the form of an elf-white solid; M.P.-1-15 C. This material was not purified but was used directly in Part Bbelow.

Part B.2-a:nilin0-4-diallylamin0-6-methyl-1,3,5- triazine Following theprocedure of Example 28, Part B,Z-anilino-4-chloro-6-methyl-1,3,5-triazine (11.0 g.; 0.05 mole) wasreacted with diallylamine (9.7 g.; 0.10 mole). The product was isolatedfrom the water-diluted reaction mixture by extraction with four 200-ml.portions of chloroform. The combined extracts were washed twice with100- ml. portions of water, and were dried with sodium sulfate.Evaporation of solvent and distillation of the residue at reducedpressure gave 10.7 g. of 2-anilino-4-diallylamino-6-methyl-l,3,5-triazine as a viscous yellow oil; B.-P C. at 1.1 mm.

.Analysis.-Calcd. for C H N C, 68.30; H, 6.81; N, 24.89. Found: C,68.48; H, 7.04; N, 24.65.

Part C.1,2-dihydro-I-hydroxy-4-diallylamin0-6-methyl-2-phenylimin0-1,3,5-triazine Following the procedure of Example25, Part B, 2-anilino-4-diallylamino-6-methyl-l,3,5-triazine (10.5 g.;0.037 mole) was oxidized with m-chloroperbenzoic acid (91.5% pure; 14.0g.; 0.074 mole) in a mixture of 100 ml. of absolute ethanol and 100 ml.of methanol. The reaction mixture was stirred for an additional 15 hoursat 25 C. The reaction product was recrystallized twice from hexane togive 2.1 g. of l,Z-dihydro-l-hydroxy-4-diallylamino-6-methyl-2-phenylimino-l,3,5-triazine in the form of tan needles whichgave a dark brown ferric chloride test; M.P. 103-105 C.

Analysis.Calcd. for C H N O: C, 64.62; H, 6.44; N, 23.55. Found: C,64.91; H, 6.41; N, 23.53. U.V.- (H 0) 259 mg (e=24,200); 304 m (sh.)(e=5,-150). (0.01 N H 80 208 my. (end absorption); 251 my. (s=20,250).(0.01 N KOH) 259 m (e=24,100); 305 mg (sh.) (e=5,250). I.R.-(Principalbands; mineral oil mull) 3060, 3050, 1618, 1600, 1575, 1520, 1495, 1185,1175, 750, 686 cm.'-

EXAMPLE 30 Part A.--2-benzylamino-4-chl0ro-6-methyl-1,3,5-triazine PartB.-2-benzylamino-4-diallyIamin0-6- methyl-1,3,5-triazine Following theprocedure of Example 28, Part B, 2- benzylamino 4 chloro 6 methyl 1,3,5triazine (11.7 g.; 0.05 mole) was reacted with diallylamine (9.7 g.;0.10 mole). The solid which precipitated from the water-diluted reactionmixture was filtered and recrystallized from hexane to give 10.9 g. of2-benzylamino-4-diallylamino-6- methyl-l,3,5-triazine in the form ofoil-white needles; M.P. 6769 C.

'27 Analysis.-Calcd. for C H N C, 69.12; H, 7.17; N, 23.71. Found: C,69.63; H, 7.01; N, 22.97. U.V. (C H OH) 226 my (e=37,550); 265 m(e=5,450). I.R.(Principal bands; mineral oil mull) 3260, 3130, 3090,1639, 1610, 1562, 1530, 1246, 1225, 734, 692 cmr PartC.I,2-dihydr0-1-hydroxy-2-benzylimino-4-diallylamin0-6-methyl-1,3,5-triazine Following the procedure of Example25, Part B, 2- benzylamino 4 diallylamino 6 methyl 1,3,5 triazine (7.4g.; 0.025 mole) was oxidized with m-chloroperbenzoic acid (91.5% pure;9.4 g.; 0.05 mole). The reaction mixture was stirred for an additional15 hours at 25 C. Solvent was removed, and the reaction residue wastreated with water and aqueous sodium hydroxide solution. The solidwhich precipitated was filtered and recrystallized twice from hexane togive 3.85 g. of 1,2- dihydro 1 hydroxy 2 benzylimino 4 diallylamino-6-methyl-1,3,5-triazine in the form of a white solid which gave a browncolor to ethanolic ferric chloride; M.P. 84 86 C. (sintered at 75 C.).

Analysis.--Calcd. for C17H21N5OZ C, 65.57; H, 6.80; N, 22.49; 0, 5.14.Found: C, 65.94; H, 7.45; N, 22.02; 0, 5.89. U.V.(H O) 225 m (e=25,l50);255 my (e=l5,750); 302 my (e=6,100). (0.01 N H 50 212 m (sh.)(e=22,850); 218 m (e=23,350); 227 m (e=23,400); 248 m (sh.) (e=16,000);276 my (sh.) (e=5,850). (0.01 N KOH) 225 m (e=24,700); 255 my(e=15,500); 302 my (e=6,050). I.R.-(Principal bands; mineral oil mull)3185, 3080, 3035, 1630, 1590, 1530, 1492, 1250, 1180, 765, 691 cmr-Following the procedure of Hirt et al., Helv. Chim. Acta 33, 1368 (1950)-in reacting Grignard reagents with cyanuric chloride, using as theGrignard reagent,

Z-naphthylmagnesium bromide;

pentylmagnesium chloride;

tert-butylmagnesium chloride; cyclopentylmagnesium bromide;2,4-dimethylphenylmagnesium bromide; o-ethylphenethylmagnesium bromide;2-methyl-3-pentenylmagnesium chloride; 4-fluoro-1-nap'hthylmethylmagnesium chloride; and 4-methyl-1-naphthylmagnesiumbromide; I there are obtained 2,4-dichloro-6-(2-naphthyl)-1,3 ,5-triazine; 2,4-dichloro-6-pentyl- 1,3 ,5-triazine;2-tert-butyl-4,6-dichloro-1,3,5-triazine; 2-cyclopentyl-4,6-dichloro-l,3 ,5 -triazine; 2,4-dichloro6- 2,4-d-imethylphenyl -1 ,3 ,5 -triazine;2,4-dichloro-6- (o-ethylphenethyl -1,3 ,S-tniazine; 2,4-dichloro-6-(2-methyl-3-phentenyl)-1,3 ,5 -triazine; 2,4-dichloro-6-(4-fiuoro-l-naphthylmethyl) -l ,3 ,5

triazine; and 2,4-dichloro-6- (4-methyl-l-naphthyl) -1,3 ,5 -triaz.ine,

respectively.

Following the procedure of Example 28, Part A, but substituting for thecombination of 2,4-dichloro-6-methyl-1,3,5-triazine and allylamine asreactants, one of the other dichloro-1,3,5-triazines listed above, inthe order listed, and one of the following primary amines in the orderlisted: sec-butylamine; isopentylarnine; octylamine; 4-hexenylamine;cyclooctylamine; l-naphthylamine; phenethylamine; 4-phenylbutylamine;and 2-naphthylmethylamine, there are obtained2-sec-butylamino-4-chloro-6-(2-naphthyl)-1,3,5-

triazine; 2-ehloro-4-isopentylamino-6-pentyl-1,3,5-triazine;2-tert-butyl-4-chloro-6-octylamino-1,3,5-triazine;2-chloro-4-cyclopentyl-6-(4-hexenylamino)-1,3,5-

triazine; 2-chloro-4cyclooctylamino-6-(2,4-dimethylphenyl)-1,3,5-triazine;

2-chloro-4- (o-ethylphenethyl) -6-( 1-naphthylamino)- 1,3 ,5 -triazine;

2-chloro-4- (2-methyl-3 -pentenyl -6-phenethylamino- 1,3 ,S-triazine;

2-chloro-4- (4-fiuoro-1-naphthylmethyl -6- (4-phenylbutylam-ino) -1,3 ,5-triazine; and

2-chloro-4-(4-methyl-1-naphthyl) -6-(2-naphthylmethylamino 1,3,5-triazine, respectively.

Following the procedure of Example 28, Part B, but substituting for thecombination of 2-allylamino-4-chloro-6- methyl-1,3,5-triazine anddiallylamine as reactants, one of the other monochloro-l,3,5-triazineslisted above, in the order listed, and one of the following secondaryamines in the order listed:

diisobutylamine dioctylamine; N-ethyl-4-pentenylamine; azet-idine;

heptamethylenimine; octamethylenimine; 2,2-dimethylpyrrolidine;2-methyl-5-ethylpiperidine; and 2,6-dimethyl-4-octy1piperidine,

there are obtained Z-sec-butylamino-4-diisobutylamino-6- Z-naphthyl 1,3,5 -tr-iazine; 2-dioctylamino-4-isopentylamino-G-pentyl-1,3 ,5-triazine; 2-tert-buty1-4- (N-ethyl-4-pentenylamino-6-octylamino-1,3,5-triazine;

2-( l-azetidinyl -4-cyc1opentyl-6- (4-hexenylamino 1,3,5-triazine;

2-cyelooctylarnino-4- (2,4-dimethylphenyl -6-( l-he ptamethylenimino)-1,3 ,5 -triazine;

2-(o-ethylphenethyl)-4-(l-naphthylamino)-6-(1-octamethylenimino)-1,3,5-triazine;

2- (2,2-dimethyl-1-pyrrolidinyl)-4-(2-methyl-3-pentenyl)-6-phenethylamino-1,3,5-triazine;

2-(4-fiuoro-1-naphthylmethyl )-4-(2-methyl-5-ethylpi-peridino-6-(4-phenylbutylamino l ,3,5-triazine; and

2- (2,6-dimethyl-4-octylpiperidino) -4-(4-methyl-1-naphthyl)-6-(2-naphthylmethylamino)-1,3,5-triazrine, respectively.

Following the procedures of Part B of Examples 1, 4, 15, or 25 butsubstituting for the 1,3,5-triazines used as reactants therein, one ofthe other diamino-l,3,5-triazines listed above, in theorder listed,there are obtained 29 EXAMPLE 3 1 1 ,Z-dihydro-I-hydroxy-2-acetylimino-4-diallylamin-6-methyl-1,3,5-triazine Acet-icanhydride (3 drops) was added with swirling to a suspension ofl,Z-dihydro-l-hydroxy-4-diallylamino- 2-imino-6-methyl-1,3,5-triazine(400 mg.) in 5 ml. of anhydrous diethyl ether. A clear solution formedrapidly, after which a crystalline solid precipitated. Filtration gave450 mg. of 1,Z-dihydro-l-hydroxy-2-acetylimino-4-diallylamino-6-methyl-1,3,5-triazine acetic acid addition salt; M.P.91-92 C.

Analysis.Calcd. for C14H31N5o4: C, H, N, 21.66. Found: C, 52.71; H,6.47; N, 21.60. U.V.-- (H 0) 235 mp. (e=15,750); 273 mp. (e=19,100); 314my. ($11.) (e=3,300). (0.01 N H3504) 227 my. (6 18, 950); 259 mu (e-15,500); 318 m (sh.) (=1,700). (0.01 N KOH) 262 mu (e=24,350); 313 m(e=4,350). I.R.-(Principal bands; mineral oil mull) 3180, 3070, 1737,1620, 1560, 1520, 1280, 1180 cmr N.M.R.- (CDCI in c.p.s. downfield fromtetramethylsilane) CCH 156; NCOCH 148; CH COOH, 119.

Addition of one molecular equivalent of triethylamine to an absoluteethanol solution of the above acetic acid addition salt, followed byevaporation and recrystallization from acetonitrile gives the free baseform of 1,2-dihydro 1 hydroxy 2 acetylimino 4 diallylamino-6-methyl-1,3,5-triazine.

Addition of one molecular equivalent of hydrogen chloride to an absoluteethanol solution of the free base form of1,2-dihydro-1-hydroxy-2-acetylimino-4-cliallylamino-6-methyl-1,3,5-triazine,followed by addition of several volumes of anhydrous diethyl ether,gives the corresponding hydrochloric acid addition salt. Using in placeof the hydrogen chloride, benzoic acid; lactic acid; succinic acid;sulfuric acid; and phosphoric acid, the corresponding acid additionsalts are obtained.

Following the procedure of Example 31 but using acetyl chloride in placeof acetic anhydride, there is obtained 1,2 dihydro 1 hydroxy 2acetylimino 4- diallylamino-6-methyl-l,3,5-triazine hydrochloric acidaddition salt.

Also following the procedure of Example 31 but using in place of theacetic anhydride, propionic anhydride; crotonic anhydride;cyclohexanecarboxylic anhydride; isobutyryl chloride; decanoyl chloride;phenylacetyl chloride; 3-methoxybutyric anhydnide;p-tert-butylcyclohexanecarbonyl chloride; and p-nitrophenylacetylchloride, there are obtained1,Z-dihydro-l-hydroxy-4-diallylamino-6-methyl-2-propionylimino-l,3,5-triazine; 1 ,Z-dihydrol-hydroxy-2-crotonoylimino-4-diallylamino6-methyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-2-cyclohexanecarbonylimino-4-diallylamino-6-methyl-l,3,5-triazine;1,Z-dihydro-1-hydroxy-4dial1ylamino-2-isobutyrylimino-6-methyl-l,3,5-triazine;1,Z-dihydro-1-hydroxy-2-decanoylimino-4-diallylamino-6-methyl-1,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-6-methyl-2-phenylacetylimino-1,3,S-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-2-(3-methoxybutyrylimino)-6-methyl-1,3,5-triaz.ine;1,2-dihydro-1-hydroxy-2-(p-tert-butylcyclohexanecarbonylimino)-4-diallylamino-6-methyl-1,3 ,5 triazine; and1,Z-dihydro-1-hydroxy-4-diallylamino-6-methyl-2-(pnitrophenylacetylimino)-1,3,5-triazine,respectively. Also following the procedure of Example 31 but using inplace of the 1,Z-dihydro-l-hydroxy-4-diallylarnino-2imino-6-methyl-1,3,5-triazine reactant,1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-1,3,5-

triazine;

30 1,2-dihydro-1-hydroxy-4-dipropylamino-2-imino-6-methyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-G-ethyl-Z-imino- 1,3,5-triazine;1,Z-dihydro-1-hydroxy-Z-imino-6-methyl-4-morpholino- 1,3,5-triazine;1,Z-dihydro-1-hydroxy-6-benzyl-4-diallylamino-2-imino- 1,3,5-triazine;l,Z-dihydro-1-hydroxy-6-butyl-4-diallylamino-2-imino- 1,3,5-triazine; 1,Z-dihydro-1-hydroxy-6-cyclohexyl-4-diallylamino-2-imino-1,3,5-triazine; 1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6-phenyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-2-imino-6-(2-methoxyethyl)-1,3,5-triazine;l,Z-dihydro-1-hydroxy-4-diallylamino-2-imino-6-(2-methoxypropyl)-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylarnino-2-imino-6-vinyl- 1,3,5-triazine;1,Z-dihydro-1-l1ydroxy-4-diallylamino-Z-imino-6-propyl- 1,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6-isopropyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-Z-imino-6-penty1- 1,3,5-triazine;1,Z-dihydro-1-hydroxy-6-p-chlorobenzyl-4-diallylamino-2-imino-1,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-2-imino-6-phenethyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-2-imino-6-(3-phenylpropyl)-l,3,5-triazine; and 1,Z-dihydrol-hydroxy-6-cyclopropyl-4-diallylamino-2-imino-l,3,5-triazine,

there are obtained 1,Z-dihydro-1-hydroxy-4-dlallylamino-Z-aoetylimino-1,3,5-triazine; 1,Z-dihydro-1-hydroxy-4-dipropylamino-2-aoetylimino-6-methyl-1,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-6-ethyl-2-acetylimino-1,3,5-triazine;1,Z-dihydro-1-hydroxy-2-acetylimino-6-methyl-4-morpholino-l,3,5-triazine;1,Z-dihydro-1-hydroxy-6-benzyl-4-diallylamino 2-acetylimino-l,3,5-triazine;1,2-dihydro-l-hydroxy-6-butyl-4-diallylamino-2-acetylimino-1,3,5-triazine;1,2-dihydro-1-hydroxy-6-cyclohexyl-4-diallylamino-2-acetylimino-1,3,5-triazine;1,Z-dihydro-1-hydr0xy-4diallylamino-2-acetylimino-6-phenyl-l,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-Z-acetylimino-6-(2-methoxyethyl)-1,3,5-triazine;1,2-dihydno-1-hydroxy-4-diallylamino-2-acetylimino-6-(2-methoxypropyl)-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-Z-acetylimino-6-vinyl-1,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-Z-acetylimino-6-propyl-1,3,5-triazine;1,Z-dihydro-1-hydroxy-4-diallylamino-Z-acetylirnino-6-isopropyl-l,3,5-triazine;1,2'dihydro-1-hydroxy-4-diallylamino-Z-acetylimino-6-pentyl-1,3,5-triazine;1,2-dihydro-1-hydroxy-6-p-chlorobenzyl-4-diallylamino-2-acetylirnino-l,3,5-triazine;1,2-dihydro-1-hydroxy-4-diallylamino-Z-acetylimino- 6-phenethyl-l ,3 ,5-triazine; 1,Z-dihydro-1-hydroxy-4-diallylamino-Z-acetylimino-6-(3-phenylpropyl)-1,3,5-triazine; and 1,2-dihydro-1-hydroxy-6-cyclopropyl-4-diallylamino- Z-acetylimino-1,3,5-triazine;respectively,

each in the form of the acetic acid addition salt; Each correspondingfree base is obtained by neutralization of 31 the acid addition saltwith triethylamine as described above.

Also following the procedure of Example 31 but using in place of the1,2-dihydro1-hydroxy-4-diallylamino-2- irnino-6-methyl-l,3,5-tr=iazinereactant, each of the specific 1,Z-dihydro-l-hydroxy-Z-imino-1,3,5triazines mentioned above, and using in place of the acetic anhydride,each of the specific carboxy-acylating agents mentioned above, there areobtained the corresponding Z-N-carboxyacylatedl,2-dihydro-l-hydroxy-l,3,5-triazines, in the form of the hydrochloricacid addition salt in the case of the carboxylic acid chloride agents,and in the form of the corresponding organic carboxylic acid additionsalt in the case of the carboxyl-ic acid anhydride agents. These acidaddition salts are each transformed to the corresponding free base byneutralization with triethylamine as described above.

EXAMPLE 321,Z-dihydro-I-acetxy-2-acetylimino-4-diallylamino-6-methyl-1,3,5-triazineFollowing the procedure of Example 31 but using one ml. of aceticanhydride, ml. of diethyl ether, heating the resulting mixture underrefiux for 4 hours, and evaporating under reduced pressure, there isobtained 1,2-dihydro l acetoxy 2 acetylimino 4 diallylamino-6-methyl-l,3,5-triazine acetic acid addition salt. The correspondingfree base is obtained by neutralization of the acid addition salt withtriethylamine as described above.

Following the procedure of Example 32 but using in place of aceticanhydride, propionic anhydride; crotonic anhydride;cyclohexanecarboxyl-ic anhydride; 3-methoxybutyric anhydride; and furoicanhydride, there are obtained 1,2-dihydro-1-(B-methoxybutyryloxy)-4-diallylamino-2-(3-methoxybutyrylimino)-6-methyl-l,3,5-triazine;

and 1,2-dihydro-1-furoyloxy-4-diallylamino-Z-furoylimino-6-methyl-l,3,5-tr-iazine, respectively,

in the form of the corresponding acid addition salt. Each acid additionsalt is transformed to the corresponding free base by neutralizationwith triethylamine as described above.

Also following the procedure of Example 32 but using in place of the1,2-dihydro-1-hydroxy-4-diallylamino-2- imino-6-methyl-l,3,5-triazinereactant, each of the 1,2-dihydro 1 hydroxy 2 imino 1,3,5 triazinesmentioned above, there are obtained the corresponding 1,2- dihydro lacetoxy 2 acetylimino 1,3,5 triazines in the form of the acetic acidaddition salts, each of which is transformed to the corresponding freebase by neutralization with triethylamine as described above.

I claim:

1. A compound selected from the group consisting of the free base formand acid addition salts of a compound of the formula:

N Rl f YN -Ra wherein R is selected from the group consisting ofhydrogen, lower alkyl, lower alkenyl, lower alkoxyalkyl, lowercycloalkyl, lower aryl, lower alkaryl, lower aralkyl, lower alkaralkyl,lower alkoxyaralkyl, and lower haloaralkyl; wherein R is selected fromthe group consisting of di-lower-alkylamino, di-lower-alkenylarnino,N-loweralkyl-lower-alkenylamino, and the heterocyclic moieties,aziridinyl, azetidinyl, pyrrolidinyl, piperidino, hexahydroazepinyl,heptamethylenimino, octamethylenimino, and morpholino, each of saidheterocyclic moieties having attached as substituents on carbon atomsthereof zero to 3 lower alkyls, inclusive, the nitrogen atom of R beingthe point of attachment of R to the ring in said formula; and wherein Ris selected from the group consisting of hydrogen, lower alkyl, loweralkenyl, lower cycloalkyl, lower aryl, and lower aralkyl.

2. A compound selected from the group consisting of the free base formand acid addition salts of a compound of the formula:

N Rr-H %NH N N \l/ R:

wherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, andlower haloaralkyl; and wherein R is selected from the group consistingof di-lower-alkylamino, di-lower-alkenylamino, N- lower alkyl loweralkenylamino, and the heterocyclic moieties, aziridinyl, azetidinyl,pyrrolidinyl, piperidino, hexahydroazepinyl, heptamethylenimino,octamethylenimino, and morpholino, each of said heterocyclic moietieshaving attached as substituents on carbon atoms thereof zero to 3 loweralkyls, inclusive, the nitrogen atom of R being the point of attachmentof R to the ring in said formula.

3. A compound selected from the group consisting of the free base formand acid addition salts of a compound of the formula:

wherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, andlower haloaralkyl; wherein R is di-lower-alkenylamino; and wherein R isselected from the group consisting of hydrogen, lower alkyl, loweralkenyl, lower cycloalkyl, lower aryl, and lower aralkyl.

4. A compound selected from the group consisting of the free base formand acid addition salts of a compound of the formula:

wherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyaralkyl, andlower haloaralkyl; and wherein R is di-lower-alkenylamino.

5. 1,2 dihydro 1 hydroxy 4 diallylamino 2- imino-l,3,5-triazine.

6. 1,2 dihydro 1 hydroxy 4 diallylamino 2- m n -fi-methyl-1,3,5-triazine7. 1,2 dihydro 1 hydroxy 4 dipropylamino 2-imino-6-methyl-1,3,5-triazine.

8. 1,2-dihydro 1 hydroxy 4 diallylamino 6 ethyl-2-imino-1,3,5-triazine.

9. 1,2-dihydro 1 hydroxy-Z-imino-6-methyl-4-morpholino-1,3,5-triazine.

10. 1,2-dihydro 1 hydroxy-6-benzyl-4-diallylamino- 2-imino1,3,5-nria.zine.

11. 1,24lihydro 1 hydroxy-6-butyl-4-diallylamino-2-imino-l,3,5-triazine.

12. 1,2-dihydro 1 hydroxy- 6 cyclohexyl-4-diallylamino-Z-imino-l ,3 ,5-triazine.

13. 1,2-dihydro 1 hydroxy-441iallylamino-2-imino-6-phenyl-1,3,5-triaz.ine.

14. 1,2-dihydro l hydroxy-4-dial-lylamino-2-imino-6-(Z-methoxyethyl)-l,3,5-triazine.

15. 1,2-dihydro 1 hydroxy-4-diallylamino-Z-irnino- 6 Z-methoxypropyl)-1,3,5-triazine.

16. 1,2-dihydro 1 hydroxy-4-diallylamino-2-imino- 6-vinyl-1,3,5triazine.

17. 1,2-di'hydro 1 hydroxy-4-diallylamino-2-imino- 6-propyl1,3,5-triazine.

18. 1,2-dihydro 1 hydroxy-4-diallylamino-2-irnino-6-isopropyl-1,3;5-triazine.

19. 1,2-dihydro 1 hydroxy-4-diallylamino-2-imino-6-pentyl-1,3,5-t.riazine.

20. 1,2-dihydro 1hydroxy-6-p-chlorobenzyl-4-diallylamino-Z-imino-1,3,5-triazine.

21. 1,2-dihydro 1 hydroxy-4-diallylamino-2-imino-6-phenethyl-l,3,5-triazine.

22. 1,2-dihydro 1 hydroxy-4-diazllylamino-2-imino-6- (3-phenylpropyl)-1,3,5-triazine.

23. 1,2-dihydro 1hydroxy-6-cyclopropyl4-diallylamino-2-imino-1,3,-5-triazine.

24. 1,2-dihydro 1 hydroxy -2allylimino-4-diallylamino-6-methyl-'1,3,5-triazine.

25. 1,2-dihydro 1 hydroxy-4-diallylamino-6-methyl-2-pheny1imino-1,3,5-triazine.

26. 1,2-dihydro 1hydroxy-Z-benzy'limino-4-dia1lylamino-6-methy1-1,3,5-triazine.

34 27. A compound of the formula:

wherein R is selected from the group consisting of hydrogen, loweralkyl, lower alkenyl, lower alkoxyalkyl, lower cycloalkyl, lower aryl,lower alkaryl, lower aralkyl, lower alkaralkyl, lower alkoxyara'lkyl,and lower haloaralkyl; wherein R is selected from the group consistingof di-lower-alkylamino, di-lower-a'lkenylamino, N-loweralkyllower-alkenylamino, and the heterocyclic moieties, aziridinyl,azetidinyl, pyrrolidinyl, piperidino, hexahydroazepinyl,heptamethylenimino, octamethylenimino, and morpholino, each of saidheterocyclic moieties having attached as substituents on carbon atomsthereof zero to 3 lower alkyls, inclusive, the nitrogen atom of R beingthe point of attachment of R to the ring in said formula; wherein A isca'rboxyacyl, and wherein A is selected from the group consisting ofhydrogen and carboxyacy'l.

28. 1,2-dihydro 1 hydroxy 2acetylimino-4-diallylamino-6-methy1-1,3,5-triazine.

29. 1,2 -dihydro 1hydroxy-Z-acetylimino-4-diallylamino-6-methyl-1,3,5-triazine acetic acidaddition salt.

Fuson: Reactions of Organic Compounds, Wiley and Sons, Inc., New York(1962), pp. 336-7.

Morrison and Boyd: Organic Chemistry, Allyn and Bacon, Inc., Boston(1959), pp. 474, 480-1.

WALTER A. MODANCE, Primary Examiner.

JOHN M. FORD, Assistant Examiner.

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE FREE BASE FORMAND ACID ADDITION SALTS OF A COMPOUND OF THE FORMULA:
 27. A COMPOUND OFTHE FORMULA: